[0001] The present invention relates to method for producing a novel polyamide-based film
and a polyamide-based film obtainable by the same. Moreover, the present invention
relates to a laminate and a container including the above-mentioned polyamide-based
film.
[0002] Various types of resin films are formed into packages and various other types of
products by undergoing various processing. For example, vinyl chloride film is used
in packages (press-through packs) for containing pharmaceuticals (tablets), etc. In
addition, polypropylene film is used in the case of packaged contents requiring protection
from moisture, for example. Recently, laminates in which metal foil is laminated on
a resin film are being used for the purpose of imparting even better gas impermeability
and moisture-proofing from the viewpoint of maintaining content quality. For example,
a laminate formed of "base layer(resin film)/metal foil layer(aluminum foil)/sealant
layer" is known.
[0003] In industrial fields, although the outer casings of lithium ion batteries have conventionally
primarily consisted of a metal can type, this type of outer casing has been indicated
as having shortcomings such as a lack of degree of freedom with respect to shape and
difficulty in reducing weight. Consequently, a laminate formed of "base layer/metal
foil layer/sealant or a laminate formed of "base layer/additional base layer/metal
foil layer/sealant layer" has been proposed for use as an outer casing. These types
of laminates have come to be widely used due to their flexibility and greater degree
of freedom with respect to shape in comparison with metal cans, their potential for
reducing weight by reducing film thickness, and the ease by which they can be reduced
in size.
[0004] Various performance requirements are placed on laminates used in the above-mentioned
applications, and moisture resistance is an extremely important parameter. However,
metal foil such as aluminum foil that imparts moisture resistance lacks ductility
when used alone and has inferior moldability. Consequently, extensibility is imparted
to enhance moldability by using a polyamide-based film as the resin film that composes
the base layer.
[0005] In this case, moldability refers to formability during cold forming (cold processing)
of a film in particular. Namely, when producing a product by molding a film, although
molding conditions including a) hot forming that involves molding the resin after
melting by heating, and b) cold forming that involves molding the resin while still
in the form of a solid without melting, formability with respect to cold forming (and
particularly drawing molding and bulging molding) is required in the above-mentioned
applications. Cold forming is a molding method, which in addition to being superior
in terms of production speed and costs since it does not have a heating step, is also
advantageous over hot forming in that it is able to take advantage of the inherent
characteristics of resins. Consequently, polyamide-based films are being developed
for use as films suitable for cold forming.
[0006] Stretched polyamide-based films are known to be an example of such polyamide-based
films (see, for example, Patent documents 1 and 2). However, these polyamide-based
films are produced by stretching using a tubular method. Namely, not only do such
films have low productivity, but they also are unable to adequately satisfy requirements
such as thickness uniformity or dimensional stability. In the case of unevenness of
film thickness in particular, when a laminate of this film and metal foil is attempted
to be processed by cold forming, there is the risk of the occurrence of fatal defects
such as breakage of the metal foil and the formation of pinholes.
[0007] In contrast, polyamide-based films have also been proposed that are stretched using
the tenter method (see, for example, Patent documents 3 to 10). The tenter method
is advantageous to the tubular method in terms of productivity, dimensional stability
and the like. Patent document 11 describes a process for producing biaxially oriented
nylon film. Patent document 12 discloses the production of a biaxially oriented nylon
66 film. Patent document 13 describes a heat-shrinkable biaxially drawn polyamide
film and process for preparation thereof. Patent document 14 discloses a gas barrier
resin film. Patent document 15 describes a polyamide film and preparation method thereof.
[0009] However, unevenness (anisotropy) in properties in each direction of the film are
still present even in polyamide-based films stretched using the tenter method. Accordingly,
these films cannot be said to have sufficiently satisfactory performance in terms
of formability during cold forming (and particularly deep drawing molding).
[0010] A polyamide-based film 14 is produced according to a process like that shown in Fig.
1. First, a molten mixture 12 is prepared by melting a raw material 11 in a melting
and mixing step 11a. An unstretched sheet 13 is obtained by molding the molten mixture
12 into the form of a sheet by a molding step 12a. Next, the polyamide-based film
14 is obtained by biaxially stretching the unstretched sheet 13 in a stretching step
13a. Further, the polyamide-based film 14 goes through, for example, a lamination
step 14a in which a metal foil layer 15 and a sealant film 16 are laminated in that
order, whereby a laminate 17 is fabricated, and then the laminate 17 is processed
into a prescribed shape in a cold forming step 15a as secondary processing, to obtain
various types of products 18 (such as a container).
[0011] In this type of stretched polyamide-based film 14, although it is desirable to reduce
non-uniformities in properties in each direction throughout the plane thereof, it
is preferable to reduce variation in properties in at least four directions every
90 degrees (total of four directions formed of an arbitrary direction serving as a
reference (0 degrees) and directions at 45 degrees, 90 degrees and 135 degrees relative
thereto moving clockwise). In a biaxially stretched polyamide-based film as shown
in Fig. 4 for example, if a MD (direction of film flow) during biaxial stretching
is taken to be a reference direction (0 degree direction) centering on an arbitrary
point A, it is desirable to eliminate variation in properties in the four directions
formed of (a) the reference direction (0 degree direction), (b) the direction at 45
degrees relative to the MD in the clockwise direction (to be referred to as the "45
degree direction"), (c) the direction at 90 degrees relative to the MD in the clockwise
direction (TD: a direction perpendicular to the direction of film flow) (to be referred
to as the "90 degree direction"), and (d) the direction at 135 degrees relative to
the MD in the clockwise direction (to be referred to as the "135 degree direction").
[0012] In the case of supplying the laminate 17 including the stretched polyamide-based
film 14 to the cold forming step 15a, since the polyamide-based film 14 is stretched
in all directions. In the case there are variations in the properties of the polyamide-based
film in the above-mentioned four directions, it is difficult to equally stretch the
film in all directions during cold forming. Namely, since there are directions in
which the film stretches easily and directions in which it stretches with difficulty,
the metal foil breaks, delamination occurs or pinholes form. When such problems occur,
the resulting stretched film is unable to fulfill the function of a package and the
like, or there is the risk of damage to the packaged object (contents). Consequently,
it is necessary to reduce non-uniformities in properties in each direction as much
as possible.
[0013] In this case, film thickness is one of the properties that has an effect on moldability
during cold forming. In the case of cold-forming a laminate including a polyamide-based
film in which there are variations in film thickness, there is a high risk of breakage
of relatively thin portions, the formation of pinholes or the occurrence of delamination.
Accordingly, it is essential that a polyamide-based film used in cold forming be such
that the thickness thereof is controlled to be uniform throughout the entire film.
[0014] With respect to uniformity of the thickness of polyamide-based films, although thickness
uniformity is superior in the case of having stretched the film using the tenter method
in comparison with stretching using the tubular method, the thickness accuracy of
the polyamide-based films obtained according to the above-mentioned Patent documents
3 to 10 is not sufficiently satisfactory. In other words, since it is necessary to
equally stretch in four vertical, horizontal and diagonal directions as previously
described during cold forming, the film is required to have sufficient thickness uniformity
for withstanding cold forming. In particular, the effect of thickness uniformity on
moldability becomes more prominent the thinner the film thickness (and particularly,
film thickness of 15 µm or less).
[0015] In general, since it becomes easier to ensure the thickness uniformity of a film
the greater the thickness thereof, designing a film to be comparatively thick has
been considered as a means for ensuring thickness uniformity. In recent years, however,
polyamide-based films and laminates thereof used for cold forming have come to be
widely used primarily in the outer casings of lithium ion batteries, and the thickness
of polyamide-based films is being required to be further reduced accompanying requirements
for higher output, reduced size and lower costs of these batteries. However, if thickness
is reduced, it becomes that much more difficult to ensure thickness uniformity.
[0016] In this manner, although the development of a polyamide-based film is desired which,
in addition to being thinner and having superior thickness uniformity, has comparatively
little variation in properties in the above-mentioned four directions, such a film
currently yet remains to be developed.
[0017] Thus, an object of the present invention is to provide a production method for a
polyamide-based film, which in addition to having superior thickness uniformity, effectively
reduces variations in properties in the above-mentioned four directions, and to provide
a polyamide-based film obtainable thereby.
[0018] As a result of conducting extensive studies in consideration of the problems of the
prior art, the inventor of the present invention found that the above-mentioned object
can be achieved based on the finding that a polyamide-based film having unique properties
can be obtained by employing a specific production method, thereby leading to completion
of the present invention.
[0019] Namely, the present invention relates to the production method of a polyamide-based
film and the polyamide-based film obtainable thereby as defined in the claims.
[0020] The polyamide-based film of the present invention has superior thickness uniformity
in addition to superior stress balance during elongation in four directions formed
of the 0 degree direction, 45 degree direction, 90 degree direction and 135 degree
direction in the clockwise direction based on an arbitrary direction. Consequently,
in a laminate obtained by laminating the film of the present invention and metal foil,
for example, the metal foil has favorable ductility, and when carrying out drawing
molding by cold forming (and particularly deep drawing molding or bulging molding),
breakage of the metal foil, delamination, pinhole formation and the like are effectively
reduced or prevented, thereby allowing the obtaining of a high-quality product (molded
body) having high reliability.
[0021] In particular, even if the thickness is extremely thin at, for example, 15 µm or
less, the polyamide-based film of the present invention has superior thickness uniformity
and superior stress balance during elongation in the above-mentioned four directions.
As a result, a laminate obtained by laminating this film with metal foil allows the
obtaining of compact products at high output by cold forming and is advantageous in
terms of cost.
[0022] In addition, according to the production method of the present invention, a polyamide-based
film having the superior characteristics described above can be produced both efficiently
and reliably. In particular, a film having superior thickness uniformity can be provided
even if the film thickness is extremely thin at, for example, 15 µm or less. Moreover,
in the case of stretching at a comparatively low temperature, a film and laminate
can be provided that are even more suitable for cold forming as a result of being
able to more effectively maintain the inherent properties of resins.
[Brief Description of Drawings]
[0023]
[Fig. 1] Fig. 1 is a schematic diagram showing an overview of a production step and
cold processing step of the polyamide-based film of the present invention.
[Fig. 2]
Fig. 2 is a schematic diagram showing a step in which an unstretched sheet is stretched
by successive biaxial stretching according to the production method of the present
invention.
[Fig. 3]
Fig. 3 is a drawing showing a tenter stretching step as viewed from direction a of
Fig. 2.
[Fig. 4]
Fig. 4 is a drawing showing the directions in which stress is measured in a film.
[Fig. 5]
Fig. 5 is a drawing showing a sample for measuring stress in a film.
[Fig. 6]
Fig. 6 is a drawing showing directions in which average thickness is measured in a
film.
1. Polyamide-based Film
[0024] The polyamide-based film of the present invention (film of the present invention)
is a polyamide-based film, wherein
- (1) the difference (A value) between the maximum value and minimum value of the respective
stress at 5% elongation as determined by a uniaxial tensile test is 35 MPa or less
in four directions formed of a specific direction from an arbitrary point in the film
that is designated as 0 degrees and directions at 45 degrees, 90 degrees and 135 degrees
relative to the specific direction in the clockwise direction,
- (2) the difference (B value) between the maximum value and the minimum value of the
respective stress at 15% elongation as determined by the uniaxial tensile test in
the above-mentioned four directions is 40 MPa or less, and
- (3) the value of standard deviation with respect to average thickness in eight directions
formed of a specific direction from an arbitrary point in the film that is designated
as 0 degrees and directions at 45 degrees, 90 degrees, 135 degrees, 180 degrees, 225
degrees, 270 degrees and 315 degrees relative to the specific direction is 0.200 or
less.
(A) Material and Composition of Film of Present Invention
[0025] The film of the present invention is a film having a polyamide resin as the main
component thereof. Polyamide resins are polymers formed by amide bonding of a plurality
of monomers. Typical examples thereof include Nylon 6, Nylon 6,6, Nylon 6,10, Nylon
11, Nylon 12 and poly(metaxyleneadipamide). In addition, they may also be two-dimensional
or multidimensional copolymers such as Nylon 6/Nylon 6,6, Nylon 6/Nylon 6,10, Nylon
6/Nylon 11 or Nylon 6/Nylon 12. In addition, they may also be mixtures thereof. Among
the above-mentioned examples, a) homopolymers of Nylon 6, b) copolymers containing
Nylon 6, or c) mixtures thereof are preferable from the viewpoints of cold formability,
strength, cost, and the like.
[0026] There are no particular limitations on the number average molecular weight of the
polyamide resin, and although it can be varied corresponding to such factors as the
type of polyamide resin used, it is normally about 10,000 to 40,000 and particularly
preferably about 15,000 to 25,000. The use of a polyamide resin having a number average
molecular weight within these ranges makes it possible to more reliably avoid crystallization
which may occur in the case of stretching at a comparatively high temperature, resulting
decreases in cold formability and the like, as a result of facilitating stretching
at a comparatively low temperature.
[0027] The content of polyamide resin in the film of the present invention is normally 90%
by mass to 100% by mass, preferably 95% by mass to 100% by mass and more preferably
98% by mass to 100% by mass. Namely, components other than polyamide resin may be
contained as necessary in a range that does not substantially adversely affect the
advantages of the present invention. For example, one type or two or more types of
various additives such as bending and pinhole resistance improving agents such as
polyolefins, polyamide elastomers or polyester elastomers as well as pigments, antioxidants,
ultraviolet absorbers, preservatives, antistatic agents or inorganic particles may
be added. In addition, at least one type of various types of inorganic lubricants
and organic lubricants may be contained as lubricants for imparting slippage. Examples
of methods used to add these lubricants (particles) include containing the particles
in the polyamide resin serving as raw material and adding the particles directly to
an extruding machine, and any one of these methods may be employed or two or more
methods may be employed in combination.
(B) Properties of Film of Present Invention
[0028] The film of the present invention is preferably that in which the molecular orientation
is biaxial. This type of film can basically be obtained by biaxial stretching. A biaxially
stretched film obtained by using rollers and a tenter is particularly preferable.
(B-1) Stress Properties
[0029] The film of the present invention is required to simultaneously satisfy the above-mentioned
A value and B value serving as indicators indicating that stress balance is extremely
superior when elongated during secondary processing. If the above-mentioned A value
and B value exceed the above-mentioned ranges, stress balance of the polyamide-based
film in all directions becomes poor and it becomes difficult to obtain uniform moldability.
In the case uniform moldability is not obtained, in the case of, for example, cold-forming
a laminate obtained by laminating the film of the present invention with metal foil,
since adequate ductility is not imparted to the metal foil (namely, it becomes difficult
for the polyamide-based film to follow the shape of the metal foil), there is increased
susceptibility to the occurrence of problems such as breakage of the metal foil, delamination
or the formation of pinholes.
[0030] Although the above-mentioned A value is normally 35 MPa or less, it is preferably
30 MPa or less, more preferably 25 MPa or less and most preferably 20 MPa or less.
Furthermore, although there are no limitations on the lower limit of the above-mentioned
A value, it is normally about 15 MPa.
[0031] Although the above-mentioned B value is normally 40 MPa or less, it is preferably
38 MPa or less, more preferably 34 MPa or less and most preferably 30 MPa or less.
Furthermore, although there are no limitations on the lower limit of the above-mentioned
B value, it is normally about 20 MPa.
[0032] In addition, although there are no particular limitations on stress in the above-mentioned
four directions at 5% elongation, stress in each direction is preferably within the
range of 35 MPa to 130 MPa, more preferably within the range of 40 MPa to 90 MPa and
most preferably within the range of 45 MPa to 75 MPa from the viewpoint of cold formability
of the laminate.
[0033] Although there are also no particular limitations on stress in the above-mentioned
four directions at 15% elongation, stress in each direction is preferably within the
range of 55 MPa to 145 MPa, more preferably within the range of 60 MPa to 130 MPa
and most preferably within the range of 65 MPa to 115 MPa from the viewpoint of cold
formability of the laminate.
[0034] In the film of the present invention, adequate cold formability may be unable to
be obtained in the case stress in the above-mentioned four directions at 5% elongation
and 15% elongation is not satisfied.
[0035] Stress in the film of the present invention in the above-mentioned four directions
is measured in the manner described below. First, after having conditioned the polyamide-based
film for 2 hours at 23°C and 50% RH for controlling the moisture content, as shown
in Fig. 5, an arbitrary point A on the film is designated as the center point, a reference
direction (0 degree direction) of the film is arbitrarily specified, each of the directions
at 45 degrees (b), 90 degrees (c) and 135 degrees (d) from the reference direction
(a) in the clockwise direction are designated as measuring directions, and strips
measuring 100 mm in each of the measuring directions from the center point A and 15
mm in the direction perpendicular to each measuring direction are cut out for use
as samples. For example, as shown in Fig. 5, a sample is cut out in the 0 degree direction
in the manner of a sample 41 over a range of 30 mm to 130 mm from the center point
A (measuring 100 mm long × 15 mm wide). Samples are similarly cut out for the other
directions as well. Stress at 5% elongation and 15% elongation are measured for these
samples at a tension speed of 100 mm/min using a tensile tester having a 50 N load
cell and a sample chuck attached thereto (Model AG-1S, Shimadzu Corporation). Furthermore,
there are no particular limitations on the above-mentioned reference direction, and
for example, the MD in the stretching step during film production can be used for
the reference direction.
[0036] The polyamide-based film of the present invention that satisfies the characteristic
values indicated above is a film preferably obtained by a biaxial stretching method
that includes a step in which the film is stretched by a tenter in at least one of
the longitudinal direction and transverse direction.
[0037] In general, biaxial stretching methods include simultaneous biaxial stretching in
which the stretching steps in the longitudinal direction and transverse direction
are carried out simultaneously, and successive biaxial stretching in which the stretching
step in the transverse direction is carried out after having carried out the stretching
step in the longitudinal direction. Although stretching in the longitudinal direction
is indicated as being carried out first in the previous explanation, stretching in
the longitudinal direction or stretching in the transverse direction may be carried
out first in the present invention.
[0038] The film of the present invention is preferably obtained by successive biaxial stretching
from the viewpoint of a greater degree of freedom and the like when setting stretching
conditions. Thus, the film of the present invention is preferably obtained by successive
biaxial stretching that includes a step in which the film is stretched by a tenter
in at least one of the longitudinal direction and transverse direction. In particular,
the film of the present invention is preferably produced according to the production
method of the present invention to be subsequently described.
(B-2) Average Thickness and Thickness Accuracy
[0039] In the film of the present invention, the standard deviation with respect to average
thickness in eight directions to be subsequently described, which is used as an indicator
indicating that the thickness accuracy (thickness uniformity) of the film of the present
invention is extremely high, is normally 0.200 or less, preferably 0.180 or less and
even more preferably 0.160 or less. In the case the standard deviation used as an
indicator of thickness accuracy as described above is 0.200 or less, variations in
thickness of the film surface are extremely small, and in the case of, for example,
film thickness of 15 µm or less, there are no occurrences of problems such as delamination
or pinhole formation when using a laminated obtained by laminating the film with metal
foil and carrying out deep drawing molding, thereby allowing the obtaining of favorable
moldability. In the case the standard deviation exceeds 0.200, due to the low level
of thickness accuracy, adequate ductility is unable to be imparted to the metal foil
when laminating the film with metal foil, the occurrence of delamination or pinhole
formation becomes conspicuous, and favorable moldability is unable to be obtained.
[0040] The above-mentioned thickness accuracy is evaluated in the manner described below.
After having conditioned the polyamide-based film for 2 hours at 23°C and 50% RH for
controlling the moisture content, as shown in Fig. 6, an arbitrary point A on the
film is designated as the center point and a reference direction (0 degree direction)
of the film is arbitrarily specified, followed by drawing a total of eight lines L1
to L8 each measuring 100 mm from the center point A in eight directions formed of
the reference direction (a) and a 45 degree direction (b), 90 degree direction (c),
135 degree direction (d), 180 degree direction (e), 225 degree direction (f), 270
degree direction (g) and 315 degree direction (h) relative to the reference direction
in the clockwise direction. Thickness is then measured with a length gauge (Heidenhain-Metro
MT1287, Heidenhain Corp.) for each of the lines at 10 mm intervals from the center
point (measured at 10 points). An example of measuring at the measuring points (10
points) in the case of measuring L2 in the 45 degree direction is shown in Fig. 6.
The average value of measured values obtained at a total of 80 data points obtained
by measuring all of the lines is then calculated, and the resulting value is used
as the value of average thickness followed by calculating the standard deviation with
respect to average thickness. Furthermore, there are no particular limitations on
the above-mentioned reference direction, and for example, the MD in the stretching
step during film production can be used for the reference direction.
[0041] In the present invention, although average thickness and standard deviation are only
required to be based on any single point (point A) of the polyamide-based film, in
a polyamide-based film that has been wound into a film roll in particular, average
thickness and standard deviation are more preferably the film thickness and standard
deviation within the above-mentioned ranges at any of the following three points.
These three points are formed of a) a location in or close to the center of the wound
width that corresponds to half of the wound amount, b) a location near the right end
of the wound width that corresponds to half of the wound length, and c) a location
near the left end of the wound width that corresponds to close to the end of winding.
[0042] In addition, the average thickness of the film of the present invention is preferably
30 µm or less, and in particular, preferably 25 µm or less, more preferably 15 µm
or less and most preferably 12 µm or less.
[0043] Although the film of the present invention is preferably a laminate obtained by laminating
with metal foil, and it is preferably used in cold forming applications, by carrying
out biaxial stretching using a tenter under stretching conditions that satisfy specific
conditions as described below, a biaxially oriented film can be obtained that has
superior thickness accuracy (such as thickness uniformity) and superior stress balance
when elongated in the above-mentioned four directions even in the case of a thin film.
[0044] In the case the average thickness of the film exceeds 30 µm, moldability of the polyamide-based
film per se decreases, it may be difficult to use the film for the outer casings of
compact batteries, and there is also the risk of this being disadvantageous in terms
of cost. On the other hand, although there are no particular limitations on the lower
limit of film thickness, if the film thickness is less than 2 µm, ductility imparted
to the metal foil when laminating with metal foil easily becomes inadequate and this
results in the risk of inferior moldability. Accordingly, the lower limit of film
thickness can be normally about 2 µm.
[0045] Although the polyamide-based film of the present invention is preferably in the form
of a laminate obtained by laminating with metal foil for use in cold forming applications,
use of the polyamide-based film of the present invention that satisfies the above-mentioned
properties makes it possible to impart adequate ductility to metal foil. Due to this
effect, moldability during cold forming and the like (and particularly drawing molding
(and especially deep drawing molding)) improves, breakage of the metal foil can be
prevented, and the occurrence of problems such as delamination or pinhole formation
can be reduced or prevented.
[0046] It becomes more difficult to impart adequate ductility to metal foil the lower the
thickness of the polyamide-based film. In the case of an extremely thin film having
a thickness of 20 µm or less in particular, there are variations in stress during
elongation. In addition, since thickness accuracy is low, prominent breakage of the
polyamide-based film or metal foil caused by the pressing load applied during cold
forming. In other words, since variations in stress during elongation become larger
in thinner films and variations in thickness also tend to become larger, a higher
degree of control of these parameters is required.
[0047] In this case, in the case of conventional production methods using the tubular method
or tenter method that are typically used to produce polyamide-based films, it is difficult
to produce a film having a thickness of 15 µm or less that also demonstrates little
unevenness in stress during elongation while also having high thickness accuracy.
This is also clear since only polyamide-based films having a minimum thickness of
15 µm are disclosed as specific examples in any of the above mentioned Patent documents
1 to 10.
[0048] In contrast, according to the present invention, as a result of employing a specific
production method to be subsequently described, a polyamide-based film having superior
stress balance during elongation in the above-mentioned four directions and high thickness
uniformity can be successfully provided particularly even in the case of a film having
a thickness of 15 µm or less. As a result of being able to provide this type of special
polyamide-based film, in the case of, for example, using a laminated obtained by laminating
with metal foil in an outer casing of a battery (such as a lithium ion battery), in
addition to being able to increase capacity with respect to the number of electrodes
or electrolyte and the like, this polyamide-based film is also able to contribute
to reduced size and lower costs of the battery per se.
(B-3) Boiling Water Shrinkage and Modulus of Elasticity
[0049] Boiling water shrinkage of the film of the present invention is preferably 2.0% to
5.0% in the MD and 2.5% to 5.5% in the TD and more preferably 2.0% to 4.0% in the
MD and 2.5% to 4.5% in the TD.
[0050] In addition, the modulus of elasticity is preferably 1.5% to 3.0% in the MD and 1.5%
to 2.5% in the TD, and more preferably 1.8% to 2.7% in the MD and 1.8% to 2.2% in
the TD.
[0051] The film of the present invention preferably has a boiling water shrinkage and modulus
of elasticity as mentioned above in order to impart adequate ductility to metal foil
when the film is laminated with the metal foil. Namely, in the case of having a boiling
water shrinkage and modulus of elasticity as described above, higher flexibility is
imparted to the polyamide-based film, thereby enabling the polyamide-based film to
more effectively impart ductility to the metal foil when laminating the film with
metal foil.
[0052] In contrast, in the case the boiling water shrinkage is less than 2.0%, since the
polyamide-based resin is resistant to deformation and lacks flexibility, there is
increased susceptibility to the occurrence of breakage, delamination or the like during
cold forming. In addition, if the boiling water shrinkage exceeds 5.5%, since flexibility
becomes excessively high, there is the risk of a decrease in moldability as a result
of being unable to impart adequate ductility.
[0053] If the modulus of elasticity is less than 1.5%, since flexibility becomes excessively
high, there may be the risk of a decrease in moldability as a result of being unable
to impart adequate ductility. In addition, if the modulus of elasticity exceeds 3.0%,
since flexibility is lacking, there is the risk of the occurrence of breakage, delamination
or the like during cold forming.
[0054] Measurement of boiling water shrinkage in the present invention is carried out in
the following manner. After having conditioned the polyamide-based film for 2 hours
at 23°C and 50% RH for controlling the moisture content, the MD of the film is specified,
the MD direction and the direction perpendicular thereto is designated as the transverse
direction (TD), the film is cut out into the shape of a strip measuring 150 mm in
the measuring direction from an arbitrary point (inter-reference line distance: 100
mm) and measuring 15 mm in the direction perpendicular to the measuring direction,
followed by measuring inter-reference line distance (A) and subjecting the test piece
wrapped in gauze to hot water treatment for 5 minutes at 100°C. Following treatment,
the test piece is immediately cooled with running water, drained and conditioned for
2 hours at 23°C and 50% RH followed by again measuring inter-reference line distance
(B) and calculating shrinkage according to the equation indicated below.
[0055] In addition, measurement of modulus of elasticity in the present invention is carried
out in the following manner. After having conditioned the polyamide-based film for
2 hours at 23°C and 50% RH for controlling the moisture content, the MD of the film
is specified, the direction perpendicular to MD is designated as TD, and the film
is cut out into the shape of a strip measuring 300 mm in the measuring direction from
an arbitrary point (inter-reference line distance: 250 mm) and 15 mm in the direction
perpendicular to the measuring direction, followed by measuring at a test speed of
25 mm/min using a tensile tester having a 1 kN load cell and a sample chuck attached
thereto (Model AG-IS, Shimadzu Corporation) and calculating modulus of elasticity
from the slope of a load-elongation curve.
(B-4) Relative Viscosity
[0056] Relative viscosity (25°C) of the film of the present invention is preferably 2.9
to 3.1 and more preferably 2.95 to 3.05. As a result of making relative viscosity
to be within these ranges, flexibility and strength are more effectively imparted
to the polyamide-based film and adequate ductility is imparted to metal foil when
laminated with the metal foil.
[0057] In the case relative viscosity is less than 2.9, the resulting film lacks strength,
and in addition to it becoming difficult to impart adequate ductility to metal foil
when laminating with the metal foil, there is also the risk of it being difficult
to form into the shape of a sheet. On the other hand, if the relative viscosity exceeds
3.1, flexibility of the film decreases, and in addition to greater susceptibility
to the occurrence of breakage during cold forming (during lamination with the metal
foil), pressure loss increases in the barrier filter when passing through an extruding
machine, thereby requiring excess extrusion energy and resulting in an increase in
production cost.
[0058] Measurement of relative viscosity in the present invention indicates the value obtained
using an Ubbelohde viscometer from a sample solution obtained by dissolving 0.5 g
of a polyamide-based film after stretching in 50 ml of 96% sulfuric acid at 25°C.
(C) Laminate Including Film of Present Invention
[0059] The film of the present invention can be used in various applications in the same
manner as known or commercially available polyamide-based films. In this case, the
film of the present invention can be used as is or after undergoing surface treatment,
or can be used in the form of a laminate obtained by laminating with other layers.
[0060] In the case of using in the form of a laminate, a typical example thereof is a laminate
including the film of the present invention and metal foil laminated on that film
(laminate of the present invention). In this case, the film of the present invention
and the metal foil may be laminated to as to be in direct contact, or they may be
laminated with other layers interposed there between. In the present invention, a
laminate obtained by laminating the film of the present invention, metal foil and
a sealant film in that order is particularly preferable. In this case, an adhesive
layer may or may not be formed between each of the layers.
[0061] Although the film of the present invention can be used as is, it particularly preferably
has a primer layer (anchor coat (AC) layer) on all or a portion of at least one side
of the film surface thereof. In the case of forming such a primer layer, adhesiveness
between the polyamide-based film and metal foil can be further enhanced if metal foil
is laminated onto a film surface having a primer layer after applying an adhesive
thereto. As a result, greater ductility can be imparted to the metal foil. Consequently,
in addition to the polyamide-based film or metal foil being more resistant to breakage,
the occurrence of delamination, pinhole formation or the like can be more effectively
prevented. A film including a primer layer in this manner is also included in the
polyamide-based film of the present invention. A detailed explanation of the primer
layer is provided in the section entitled "Embodiment of Primer Layer" to be subsequently
described.
[0062] Although examples of metal foil include metal foil containing various metal elements
(such as aluminum, iron, copper or nickel) (the metal foil including alloy foil),
pure aluminum foil or aluminum alloy foil is used particularly preferably. Aluminum
alloy foil preferably contains iron (in the form an aluminum-iron-based alloy, for
example), while other components may be contained within a range that does not impair
moldability of the above-mentioned laminate provided they are contained within known
content ranges defined in JIS and other standards.
[0063] Although there are no particular limitations thereon, the thickness of the metal
foil is preferably 15 µm to 80 µm and more preferably 20 µm to 60 µm.
[0064] The sealant film that composes the laminate of the present invention preferably employs
a thermoplastic resin having heat sealing ability, as represented by polyethylene,
polypropylene, olefin copolymer and polyvinyl chloride. Although there are no limitations
on the thickness of the sealant film, normally it is preferably 20 µm to 80 µm and
more preferably 30 µm to 60 µm.
[0065] In addition, the laminate of the present invention may also have one or more other
layers on the external side (side differing from the side laminated with metal foil)
of the film of the present invention that composes the laminate corresponding to the
purpose of use and the like. Although there are no particular limitations on the other
layers, a polyester film, for example, is preferable. As a result of laminating a
polyester film, in addition to being able to enhance heat resistance, withstand voltage,
chemical resistance and the like, peel strength can also be enhanced.
[0066] There are no particular limitations on the polyester and preferable examples thereof
include polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-2,6-naphthalate.
Among these, PET is used preferably from the viewpoints of cost and advantageous effect.
[0067] The laminate of the present invention can have an adhesive layer interposed between
each of the layers. For example, each layer is preferably laminated using an adhesive
layer such as a urethane-based adhesive layer or acrylic-based adhesive layer between
the polyamide-based film and metal foil, between the metal foil and sealant film,
or the like.
[0068] In this case, metal foil is preferably laminated on a primer layer when the polyamide-based
film of the present invention has a primer layer on at least one side of the film
surface thereof. More specifically, the metal foil is preferably laminated on the
primer layer with an adhesive layer such as a urethane-based adhesive layer or acrylic-based
adhesive layer interposed between the primer layer and the metal foil.
[0069] Since the laminate of the present invention contains the film of the present invention
in particular, it can be preferably used for cold forming in the form of drawing process
(and particularly deep drawing molding or bulging molding). Here, drawing molding
specifically refers to a method for molding a bottomed container having, e.g., a cylindrical,
rectangular cylindrical or conical shape from a single laminate. Such containers typically
have the characteristic of not containing seams.
(D) Container Including Laminate of Present Invention
[0070] The present invention encompasses a container including the laminate of the present
invention. For example, a container molded using the laminate of the present invention
is included in the present invention. Among these, a container obtained by cold forming
is preferable. In particular, a container produced by cold forming in the form of
drawing molding (drawing processing) or bulging molding (bulging processing) is preferable,
while a container produced by deep drawing molding is particularly preferable.
[0071] Namely, the container according to the present invention can be more preferably produced
by a method for producing a container from the laminate of the present invention that
comprises a step for cold-forming the above-mentioned laminate. Thus, a seamless container,
for example, can be produced from the laminate of the present invention.
[0072] There are no limitations on the cold forming method per se in this case, and can
be carried out in accordance with a known method. For example, a method may be employed
in which the resin contained in the laminate is molded while still in the state of
a solid without melting. Although the temperature during molding may be normal temperature,
it is preferably 50°C or lower and particularly preferably 20°C to 30°C.
[0073] Specific examples of molding methods (processing methods) that can be preferably
employed include drawing moldings such as cylindrical drawing molding, rectangular
cylindrical drawing molding, irregular shape drawing molding, conical drawing molding,
pyramidal drawing molding or ball head drawing molding. In addition, although drawing
processing is classified into shallow drawing molding and deep drawing molding, the
laminate of the present invention can also be applied to deep drawing molding in particular.
[0074] This drawing molding can be carried out using an ordinary metal mold. For example,
drawing molding can be carried out by a method that uses a press machine containing
a punch, a die and a blank holder and comprises a) a step of arranging the laminate
of the present invention between the die and blank holder, and b) a step of forming
the laminate into the shape of a container by pressing the punch onto the laminate.
[0075] Since problems such as breakage of the metal foil, delamination and pinhole formation
are efficiently inhibited in a container obtained in this manner, a high level of
reliability can be obtained. As a result, the container according to the present invention
can be used in various applications, including the packaging materials of various
types of industrial products. In particular, a molded body obtained by deep drawing
molding is preferably used for the outer casing of a lithium ion battery, while a
molded body obtained by bulging molding is preferably used for a press-through pack,
for example.
<Embodiment of Primer Layer>
[0076] The following embodiment can be adopted for the primer layer in the polyamide-based
film of the present invention.
[0077] Although there are no limitations on the thickness of the primer layer, normally
it is preferably 0.01 µm to 0.10 µm and more preferably 0.02 µm to 0.09 µm. If the
thickness of the primer layer is less than 0.01 µm, it becomes difficult to form a
primer layer of uniform thickness on the film. As a result, the effect of improving
adhesiveness between the polyamide-based film and metal foil as previously described
is inadequate. On the other hand, if the thickness of the primer layer exceeds 0.10
µm, the effect of favorable adhesiveness between the polyamide-based film and metal
foil becomes saturated, which is disadvantageous in terms of cost.
[0078] A layer including various types of synthetic resins such as polyurethane resin or
acrylic resin can be employed for the primer layer. A primer layer containing polyurethane
resin is particularly preferable. This type of polyurethane resin preferably contains,
for example, an anionic water-dispersible polyurethane resin. A primer layer containing
this resin can be formed by coating an aqueous coating agent containing the above-mentioned
resin onto the surface of the polyamide-based film.
[0079] The polyurethane resin is a polymer obtained by reacting, for example, a polyfunctional
isocyanate and a hydroxyl group-containing compound. Specific examples thereof include
urethane resins obtained by reacting a polyfunctional isocyanate, such as an aromatic
polyisocyanate such as tolylene diisocyanate, diphenylmethane isocyanate or polymethylene
polyphenylene polyisocyanate, or an aliphatic polyisocyanate such as hexamethylene
diisocyanate or xylene isocyanate, with a hydroxyl group-containing compound such
as a polyether polyol, polyester polyol, polyacrylate polyol or polycarbonate polyol.
[0080] The anionic water-dispersible polyurethane resin used in the present invention has
an anionic functional group introduced into a polyurethane resin. There are no particular
limitations on the method of introducing the anionic functional group into the polyurethane
resin, and examples thereof include a) a method that uses, for example, a diol having
an anionic functional group as a polyol component, and b) a method that uses, for
example, a diol having an anionic functional group as a chain extender.
[0081] Examples of diols having an anionic functional group include aliphatic carboxylic
acids such as glyceric acid, dioxymaleic acid, dioxyfumaric acid, tartaric acid, dimethylolpropionic
acid, dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic
acid, 4,4-di(hydroxyphenyl)valeric acid or 4,4-di(hydroxyphenyl)butyric acid, and
aromatic carboxylic acids such as 2,6-dioxybenzoic acid.
[0082] A volatile base is typically preferably used when dispersing the anionic polyurethane
resin in water. There are no particular limitations on the volatile base and a known
volatile base can be used. Specific examples thereof include ammonia, methylamine,
ethylamine, dimethylamine, diethylamine, triethylamine, morpholine and ethanolamine.
Among these, triethylamine enables favorable liquid stability of the water-dispersible
polyurethane resin and has a comparatively low boiling point, thereby making it preferable
from the viewpoint of only a small amount thereof remaining in the primer layer.
[0083] A commercially available anionic water-dispersible polyurethane resin can be preferably
used to form the primer layer. Examples of such commercially available anionic water-dispersible
polyurethane resins include Hydran ADS-110, Hydran ADS-120, Hydran KU-400SF, Hydran
HW-311, Hydran HW-312B, Hydran HW-333, Hydran AP-20, Hydran APX-101HD and Hydran AP-60LM
manufactured by DIC Corp., Superflex 107M, Superflex 150, Superflex 150HS, Superflex
410, Superflex 420NS, Superflex 460, Superflex 460S, Superflex 700, Superflex 750
and Superflex 840 manufactured by DKS Co., Ltd., Takelac W-6010, Takelac W-6020, Takelac
W-511, Takelac WS-6021 and Takelac WS-5000 manufactured by Mitsui Chemicals Polyurethanes,
Inc., and NeoRez R9679, NeoRez R9637, NeoRez R966 and NeoRez R972 manufactured by
DSM N.V.
[0084] In the polyamide-based film of the present invention, a melamine resin is preferably
contained in the primer layer in order to improve water resistance, heat resistance
and the like of the primer layer. The content of melamine resin is preferably 1 part
by mass to 10 parts by mass based on 100 parts by mass of the anionic water-dispersible
polyurethane resin.
[0085] A typical example of a melamine resin is a tri(alkoxymethyl)melamine. Examples of
the alkoxy group thereof include a methoxy group, ethoxy group, propoxy group and
butoxy group. Various types of melamine resins can be respectively used alone or two
or more types can be used simultaneously.
[0086] Although the solid content concentration of the anionic water-dispersible polyurethane
resin in the aqueous coating agent can be suitably altered according to the specifications
of the coating device, drying/heating device or the like, an excessively dilute solution
is susceptible to the occurrence of the problem of requiring a long period of time
in the drying step. On the other hand, if the solid content concentration is excessively
high, it becomes difficult to obtain a uniform coating agent, thereby resulting in
increased susceptibility to the occurrence of problems with coating properties. From
this viewpoint, the solid content concentration of the anionic water-dispersible polyurethane
resin in the aqueous coating agent is preferably within the range of 3% by mass to
30% by mass.
[0087] An additive such as an antifoaming agent or surfactant may also be added to the aqueous
coating agent in addition to the main component thereof in the form of the anionic
water-dispersible polyurethane resin in order to improve coating properties when coating
the aqueous coating agent onto the film.
[0088] Wetting of the aqueous coating agent onto the base film can be promoted by adding
a surfactant in particular. There are no particular limitations on the surfactant
and examples thereof include anionic surfactants such as polyethylene alkyl phenyl
ethers, polyoxyethylene fatty acid esters, glycerin fatty acid esters, fatty acid
metal soaps, alkyl sulfates, alkyl sulfonates or alkyl sulfosuccinates, and nonionic
surfactants such as acetylene glycol. The surfactant is preferably contained at 0.01%
by mass to 1% by mass in the aqueous coating agent. In addition, it is also preferable
that the surfactant evaporate during heat treatment in the polyamide-based film production
process.
[0089] Moreover, various types of additives such as an antistatic agent or slipping agent
can be added to the aqueous coating agent as necessary so as to not adversely affect
adhesiveness.
2. Production Method of Film of Present Invention
[0090] The production method of the present invention is a method for producing a biaxially
stretched polyamide-based film, including:
- (1) a sheet molding step for obtaining an unstretched sheet by molding a molten mixture
containing a polyamide resin into the form of a sheet, and
- (2) a stretching step for obtaining a stretched film by biaxially stretching the unstretched
sheet either successively or simultaneously in the MD and TD; wherein
- (3) the following formulas a) and b) are both satisfied:
- (a) 0.85 ≤ X/Y ≤ 0.95
- (b) 8.5 ≤ X×Y ≤ 9.5
(wherein, X represents a draw ratio in the MD and Y represents a draw ratio in the
TD), and
- (4) the stretching step includes stretching in the MD with rollers and stretching
in the TD with a tenter,
wherein the stretching step involves successive biaxial stretching comprising:
(2-1) a first stretching step of obtaining a first stretched film by stretching the
unstretched sheet in the MD at a temperature of 50°C to 120°C; and
(2-2) a second stretching step of obtaining a second stretched film by stretching
the first stretched film in the TD at a temperature of 70°C to 150°C, and
wherein the second stretched film is further subjected to relaxation heat treatment
at a temperature of 180°C to 230°C.
Sheet Molding Step
[0091] In the sheet molding step, an unstretched sheet is obtained by molding a molten mixture
containing polyamide resin into the form of a sheet.
[0092] Various types of materials can be used for the polyamide resin as previously described.
In addition, various types of additives can be contained in the molten mixture.
[0093] Preparation of the molten mixture per se may be carried out in accordance with a
known method. For example, a sheet-like molded body in the form of an unstretched
sheet can be obtained by charging a raw material containing polyamide resin into an
extruding machine equipped with a heating device, melting the raw material by heating
to a prescribed temperature followed by extruding the molten mixture from a T die,
and cooling and solidifying the mixture with a casting drum and the like.
[0094] Although there are no particular limitations thereon, the average thickness of the
unstretched sheet in this case is typically about 15 µm to 250 µm and particularly
preferably 50 µm to 235 µm. The stretching step can be carried out more efficiently
by setting average thickness to be within these ranges.
Stretching Step
[0095] In the stretching step, a stretched film is obtained by biaxially stretching the
above-mentioned unstretched sheet in the MD and TD.
[0096] As was previously described, the stretched film is obtained by successive biaxial
stretching including a step for stretching with a tenter in at least one of the MD
and TD. By this process, more uniform film thickness can be obtained.
[0097] The tenter per se is a device that has conventionally been used to stretch films,
and operates by clamping both ends of an unstretched sheet and widening in the longitudinal
direction and/or transverse direction. There are two types of stretching methods,
namely, simultaneous biaxial stretching and successive biaxial stretching also in
the case of using a tenter. Simultaneous biaxial stretching using a tenter is a method
for simultaneously carrying out biaxial stretching in the MD and TD by stretching
in the TD simultaneous to stretching in the MD while clamping both ends of an unstretched
film. On the other hand, successive biaxial stretching using a tenter includes 1)
a method for stretching an unstretched sheet in the MD by passing over a plurality
of rollers having different rotating speeds followed by stretching the stretched film
in the TD with a tenter, or 2) a method for stretching an unstretched sheet in the
MD with a tenter followed by stretching the stretched film in the TD with a tenter.
The method of 1) above is particularly preferable from the viewpoints of the properties
of the resulting film, productivity and the like. In the case of the method of 1)
above, an unstretched film is successively biaxially stretched by a process like that
shown in Fig. 2.
[0098] First, as shown in Fig. 2, an unstretched sheet 13 is stretched in the MD (longitudinal
direction) by passing over a plurality of rollers 21. Since this plurality of rollers
has different rotating speeds, the unstretched sheet 13 is stretched in the MD due
to the difference in their speeds. Namely, the unstretched sheet is stretched by passing
from a low speed roller group to a high speed roller group.
[0099] Furthermore, although five rollers are shown in Fig. 2, the actual number of rollers
may be different therefrom. In addition, rollers having mutually different functions
in the manner of preheating rollers, stretching rollers and cooling rollers can also
be installed in that order. The number of these rollers having various functions can
be set as is suitable. In addition, in the case of providing a plurality of stretching
rollers, they may be set to enable stretching in multiple stages. For example, the
draw ratio in the MD can be suitably set to be within the range of (E1 × E2) by two-stage
drawing molding using draw ratio E1 for the first stage and draw ratio E2 for the
second stage. A first stretched film 13' is obtained in this manner.
[0100] Next, the first stretched film 13' that has passed over the rollers 21 is stretched
in the TD by introducing into a tenter 22. More specifically, as shown in Fig. 3,
the first stretched film 13' that has been introduced into the tenter 22 is clamped
near the entrance of the tenter 22 at both ends by clips connected to linkages 34
mounted on guide rails, after which it passes through a preheating zone 31, a stretching
zone 32 and a relaxation heat treatment zone 33 in that order moving in the direction
of flow. After having been heated to a specific temperature in the preheating zone
31, the first stretched film 13' is stretched in the TD in the stretching zone 32.
Subsequently, relaxation treatment is carried out at a specific temperature in the
relaxation heat treatment zone 33. A second stretched film 14 (film of the present
invention) can be obtained in this manner. Subsequently, the linkages 34 mounted on
guide rails are disengaged from the second stretched film 14 near the exit of the
tenter 22 and returned to the vicinity of the entrance of the tenter 22.
[0101] In this manner, successive biaxial stretching using a tenter is advantageous in terms
of productivity, equipment and the like since the film is stretched in the MD by rollers,
and is advantageous in terms of controlling film thickness and the like since the
film is stretched in the TD with a tenter.
[0102] In the production method of the present invention, it is essential that both of the
following formulas a) and b) are satisfied:
- a) 0.85 ≤ X/Y ≤ 0.95 (and preferably, 0.89 ≤ X/Y ≤ 0.93)
- b) 8.5 ≤ X×Y ≤ 9.5 (and preferably, 8.7 ≤ X×Y ≤ 9.1) (wherein, X represents a draw
ratio in the MD and Y represents a draw ratio in the TD).
[0103] In the case either of the above-mentioned conditions of a) or b) is not satisfied,
stress balance of the resulting polyamide-based film in four directions becomes poor,
thereby making it difficult to obtain the film of the present invention.
[0104] Temperature conditions in the stretching step are preferably such that the temperature
during the above-mentioned simultaneous biaxial stretching is within the range of,
for example, 180°C to 220°C. In addition, stretching in the MD is carried out within
a temperature range of 50°C to 120°C (and particularly 50°C to 80°C, more particularly
50°C to 70°C and even more particularly 50°C to 65°C) when carrying out the above-mentioned
successive biaxial stretching, while stretching in the TD is carried out within a
temperature range of 70°C to 150°C (and particularly 70°C to 130°C, more particularly
70°C to 120°C and even more particularly 70°C to 110°C). The film of the present invention
can be produced more reliably by controlling temperature so as to be within these
ranges. These temperatures can be set and controlled while preheating with, for example,
the rollers 21 (preheating rollers) shown in Fig. 2 or the preheating zone 31 of the
tenter shown in Fig. 3.
[0105] Relaxation heat treatment is carried out after stretching for both simultaneous biaxial
stretching and successive biaxial stretching using a tenter. Relaxation heat treatment
is carried out within a temperature range of 180°C to 230°C preferably at a relaxation
rate of 2% to 5%. These temperatures can be set and controlled in the relaxation treatment
zone of the tenter shown in Fig. 3.
[0106] Although examples of means for realizing the temperature range during stretching
as described above include: 1) blowing hot air onto the film surface, 2) using a far
infrared or near infrared heater, and 3) a combination of the two, etc. and the heating
method of the present invention preferably includes a method involving blowing hot
air.
<Embodiment of Stretching Step>
[0107] A successive biaxial stretching step including stretching in the MD with rollers
and stretching in the TD with a tenter is employed for the stretching step in the
present invention. As a result of employing this method and satisfying the temperature
conditions indicated below, since it becomes possible to demonstrate superior thickness
uniformity as well as more superior stress balance during elongation in the above-mentioned
four directions, the film of the present invention having a thickness of 15 µm or
less in particular can be more reliably and efficiently obtained.
Stretching in MD
[0108] First, stretching in the MD is preferably carried out using rollers within a temperature
range of 50°C to 70°C and more preferably 50°C to 65°C.
[0109] Stretching in the MD is preferably carried out by multistage (two stages or more)
stretching. In this case, the draw ratio is preferably increased in stages. Namely,
stretching is preferably controlled so that the draw ratio of the (n+1)th stage is
higher than the draw ratio of the (n)th stage. As a result, the overall film can be
stretched even more uniformly. For example, in the case of two-stage stretching, the
draw ratio in the longitudinal direction can be suitably set within the range of 2.53
times to 3.12 times by making the draw ratio of the first stage to be 1.1 times to
1.2 times and making the draw ratio of the second stage to be 2.3 times to 2.6 times.
[0110] Moreover, a temperature gradient is preferably applied to stretching in the MD. In
particular, the temperature is preferably made to sequentially rise along the receiving
direction of the film, and the temperature gradient throughout the entire stretching
section (temperature difference between a temperature T1 at the start of the film
in the traveling direction (entrance) and a temperature T2 at the end (exit)) is normally
preferably 2°C or more and more preferably 3°C or more. At this time, the transit
time (heating time) of the film from the start (entrance) to the end (exit) of the
film in the traveling direction is normally preferably 1 second to 5 seconds and more
preferably 2 seconds to 4 seconds.
Stretching in TD
[0111] Stretching in the TD is carried out with a tenter having the zones shown in Fig.
3 is formed. At this time, the temperature of the preheating zone is preferably 60°C
to 70°C. The temperature of the stretching zone is preferably made to be within the
range of 70°C to 130°C, more preferably within the range of 75°C to 120°C, and most
preferably within the range of 80°C to 110°C.
[0112] In addition, the temperature is preferably made to sequentially rise along the receiving
direction of the film in the stretching zone, and throughout the entire stretching
zone, the temperature gradient thereof (temperature difference between a temperature
T1 at the start of the film in the traveling direction (entrance) and a temperature
T2 at the end (exit)) is normally preferably 5°C or more and more preferably 8°C or
more. At this time, the transit time (heating time) of the film from the start (entrance)
to the end (exit) of the film in the traveling direction in the stretching zone is
normally preferably 1 second to 5 seconds and more preferably 2 seconds to 4 seconds.
[0113] Relaxation heat treatment is desirably carried out in the relaxation heat treatment
zone. The heat treatment temperature thereof is within the range of 180°C to 230°C,
more preferably within the range of 180°C to 220°C and most preferably within the
range of 180°C to 210°C. In addition, the relaxation rate is normally preferably about
2% to 5%.
[0114] In addition, when obtaining the polyamide-based film of the present invention having
a primer layer on at least one side of the film surface as well, stretching is preferably
carried out using the same stretching method and same stretching conditions as previously
described. In the production method described above, an aqueous coating agent is preferably
coated onto the polyamide-based film after being stretched in the MD in order to form
the primer layer on the film surface. The film is subsequently preferably stretched
in the TD under the same conditions as previously described together with the aqueous
coating agent (inline coating). The coated amount of the aqueous coating agent is
preferably adjusted so that the thickness of the primer layer formed on the film surface
after stretching is 0.01 µm to 0.10 µm.
[0115] Furthermore, a stretching method other than that described above is preferably excluded
for the stretching step in the production method of the present invention from the
viewpoint of ensuring thickness uniformity and the like. For example, it is preferred
that a stretching step using the tubular method (inflation method) is not included
in the production method of the present invention.
Examples
[0116] The following provides a more detailed explanation of characteristics of the present
invention by indicating examples and comparative examples thereof. However, the scope
of the present invention is not limited to these examples.
Example 1
(1) Production of Polyamide-Based Film
[0117] An unstretched sheet was produced by using a Polyamide 6 resin (Unitika Ltd., A1030BRF,
relative viscosity: 3.1, monomer content: 1.0% or less) and a Silica-containing Nylon
6 resin that contains 6% by mass of silica (Unitika Ltd., A1030QW, relative viscosity:
2.7, monomer content: 1.0% or less) as raw materials, melting and kneading in an extruding
machine at a component ratio of A1030BRF/silica-containing Nylon resin of 98.7/1.3
(mass ratio), supplying the molten mixture to a T-die, discharging in the form of
a sheet, and winding around a metal drum adjusted to a temperature of 20°C followed
by cooling and taking up into a roll. At this time, the feed rate of the polyamide
resin was adjusted so that the thickness of the polyamide-based film obtained after
stretching was 12 µm.
[0118] Next, the resulting unstretched sheet was subjected to a stretching step by successive
biaxial stretching. More specifically, stretching was carried out by a method involving
stretching in the MD using rollers followed by stretching in the TD using a tenter.
[0119] First, the unstretched sheet was stretched in the MD by passing the above-mentioned
sheet over a plurality of rollers so that a total draw ratio in the MD was 2.85 times.
At this time, stretching was carried out by two-stage stretching, the draw ratio in
the first stage was 1.1 times, the draw ratio in the second stage was 2.59 times,
and the total draw ratio (MD1 × MD2) was 1.1 × 2.59 = 2.85 times. As to heating conditions,
a temperature gradient along the receiving direction of the film was set so that the
temperature (T1) at the start in the traveling direction was 54°C and the temperature
(T2) at the end was 57°C in the MD stretching. In this case, transit time (heating
time) of the film from the start (entrance) to the end (exit) of the film in the traveling
direction was about 3 seconds.
[0120] After that, stretching in the TD was carried out using a tenter as shown in Fig.
3. First, the film was stretched at a draw ratio of 3.2 times in the TD in the stretching
zone while preheating to a temperature of 65°C in the preheating zone (preheating
section). At this time, a temperature gradient along the receiving direction of the
film was created in the stretching zone (stretching section) so that the temperature
(T1) at the start of the film in the traveling direction was 74°C and the temperature
(T2) at the end was 96°C. Transit time (heating time) of the film from the start (entrance)
to the end (exit) of the film in the traveling direction was about 3 seconds.
[0121] After having passed through the stretching zone, the film was subjected to relaxation
heat treatment in the relaxation heat treatment zone (heat treatment section) under
conditions of a temperature of 202°C and relaxation rate of 3%. A biaxially stretched
polyamide-based film (wound length: 2000 m) was obtained by continuously producing
1000 m or more in this manner. The resulting film was taken up into the form of a
roll.
(2) Laminate Fabrication
[0122] After coating a two-component polyurethane-based adhesive (Toyo-Morton, Ltd., TM-K55/CAT-10L)
onto the biaxially stretched polyamide-based film obtained in (1) above to a coated
amount of 5 g/m
2, the coated film was dried for 10 seconds at 80°C. Metal foil (aluminum foil having
a thickness of 50 µm) was laminated onto the adhesive-coated surface thereof. After
coating the above-mentioned adhesive onto the aluminum foil side of the laminate formed
of the polyamide-based film and metal foil under the same conditions, a sealant film
(unstretched polypropylene film (Mitsui Chemicals Tohcello, Inc., GHC, thickness:
50 µm) was laminated on the coated side thereof followed by subjecting to aging treatment
for 72 hours in an atmosphere at 40°C to fabricate a laminate (the polyamide-based
film/aluminum foil/sealant film).
Examples 2-28 and Comparative Examples 1-16
[0123] Polyamide-based films were obtained using the same method as Example 1 with the exception
of changing the production conditions and target thickness of the stretched polyamide-based
film to those shown in Tables 1 to 3. Laminates were then fabricated in the same manner
as Example 1 using the resulting polyamide-based films. However, the changes made
in Examples 7 and 17 are described in detail below.
(1) Example 7
[0124] After coating a two-pack type polyurethane-based adhesive (Toyo-Morton, Ltd., TM-K55/CAT-10L)
onto the side of the polyamide-based film on which the aluminum foil was not laminated
in the laminate obtained in Example 1 to a coated amount of 5 g/m
2, the coated film was dried for 10 seconds at 80°C. A PET film (Unitika Ltd., Emblet
PET-12, thickness: 12 µm) was laminated onto the adhesive-coated surface thereof to
fabricate a laminate (the PET film, /polyamide-based film/ aluminum foil/sealant film).
(2) Example 17
[0125] A polyamide-based film was obtained using the same method as Example 1 with the exception
of using a composition containing Polyamide 6 resin (Unitika Ltd., A1030BRF), Polyamide
66 resin (Unitika Ltd., A226) and Silica-containing Nylon 6 resin that contains 6%
by mass of silica at a component ratio of A1030BRF/A226/Silica-containing nylon resin
of 89.0/9.7/1.3 (mass ratio) as raw material in the production of the polyamide-based
film indicated in Example 1. A laminate was fabricated in the same manner as Example
1 using the resulting polyamide-based film.
[Table 1]
|
MD |
TD |
MD/TD |
MD×TD |
Target Thickness |
Heat Treatment Temperature |
Draw Ratio |
Preheating Section |
Stretching Section |
Heat Treatment Section |
T1 |
T2 |
1st stage MD1 |
2nd stage MD2 |
Total Draw Ratio MD1×MD2 |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
Ex.1 |
54 |
57 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.2 |
54 |
57 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.30 |
202 |
3 |
0.86 |
9.4 |
12 |
Ex.3 |
54 |
57 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.05 |
202 |
3 |
0.93 |
8.7 |
12 |
Ex.4 |
54 |
57 |
1.1 |
2.68 |
2.95 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.92 |
9.4 |
12 |
Ex.5 |
54 |
57 |
1.1 |
2.48 |
2.73 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.85 |
8.7 |
12 |
Ex.6 |
54 |
57 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.20 |
213 |
3 |
0.89 |
9.1 |
12 |
Ex.7 |
Used polyamide-based film of Example 1 |
Ex.8 |
58 |
61 |
1.1 |
2.59 |
2.85 |
70 |
78 |
100 |
3.20 |
202 |
4 |
0.89 |
9.1 |
15 |
Ex.9 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.20 |
202 |
3 |
0.89 |
9.1 |
10 |
Ex.10 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.30 |
202 |
3 |
0.86 |
9.4 |
10 |
Ex.11 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.05 |
202 |
3 |
0.93 |
8.7 |
10 |
Ex.12 |
52 |
55 |
1.2 |
2.46 |
2.95 |
64 |
72 |
95 |
3.20 |
202 |
3 |
0.92 |
9.4 |
10 |
Ex.13 |
52 |
55 |
1.2 |
2.28 |
2.74 |
64 |
72 |
95 |
3.20 |
202 |
3 |
0.85 |
8.7 |
10 |
Ex.14 |
52 |
55 |
1.2 |
2.38 |
2.86 |
64 |
72 |
95 |
3.20 |
213 |
3 |
0.89 |
9.1 |
10 |
[Table 2]
|
MD |
TD |
MD/TD |
MDxTD |
Target Thickness |
Heat Treatment Temperature |
Draw Ratio |
Preheating Section |
Stretching Section |
Heat Treatment Section |
T1 |
T2 |
1st stage MD1 |
2nd stage MD2 |
Total Draw Ratio MD1×MD2 |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
Ex.15 |
60 |
64 |
1.2 |
2.38 |
2.85 |
78 |
84 |
104 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
Ex.16 |
50 |
54 |
1.1 |
2.59 |
2.85 |
63 |
70 |
94 |
3.20 |
202 |
5 |
0.89 |
9.1 |
8 |
Ex.17 |
60 |
64 |
1.1 |
2.59 |
2.85 |
70 |
90 |
110 |
3.20 |
202 |
5 |
0.89 |
9.1 |
12 |
Ex.18 |
59 |
63 |
1.05 |
2.71 |
2.85 |
70 |
78 |
100 |
3 |
202 |
4 |
1 |
9 |
15 |
Ex.19 |
58 |
61 |
1.1 |
2.59 |
2.85 |
69 |
76 |
102 |
3.20 |
202 |
3 |
0.89 |
9.1 |
15 |
Ex.20 |
55 |
58 |
1.05 |
2.71 |
2.85 |
65 |
74 |
96 |
3 |
202 |
3 |
1 |
9 |
12 |
Ex.21 |
54 |
57 |
1.1 |
2.59 |
2.85 |
65 |
73 |
98 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.22 |
55 |
58 |
1.05 |
2.81 |
2.95 |
65 |
74 |
96 |
3 |
202 |
3 |
1 |
9 |
12 |
Ex.23 |
54 |
57 |
1.1 |
2.68 |
2.95 |
66 |
75 |
95 |
3.20 |
202 |
3 |
0.92 |
9.4 |
12 |
Ex.24 |
70 |
74 |
1.2 |
2.38 |
2.85 |
78 |
84 |
104 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
Ex.25 |
60 |
64 |
1.2 |
2.38 |
2.85 |
78 |
90 |
115 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
Ex.26 |
54 |
57 |
1.1 |
2.59 |
2.85 |
70 |
90 |
121 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.27 |
68 |
70 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.28 |
68 |
70 |
1.1 |
2.59 |
2.85 |
70 |
90 |
121 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
[Table 3]
|
MD |
TD |
MD/TD |
MD×TD |
Target Thickness |
Heat Treatment Temperature |
Draw Ratio |
Preheating Section |
Stretching Section |
Heat Treatment Section |
T1 |
T2 |
1st stage MD1 |
2nd stage MD2 |
Total Draw Ratio MD1×MD2 |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
Comp.Ex.1 |
54 |
57 |
1.1 |
2.33 |
2.56 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.8 |
8.2 |
12 |
Comp.Ex.2 |
54 |
57 |
1.1 |
2.55 |
2.80 |
65 |
74 |
96 |
3.60 |
202 |
3 |
0.78 |
10.1 |
12 |
Comp.Ex.3 |
54 |
57 |
1.1 |
2.55 |
2.80 |
65 |
74 |
96 |
2.80 |
202 |
3 |
1.00 |
7.8 |
12 |
Comp.Ex.4 |
54 |
57 |
1.1 |
2.91 |
3.20 |
65 |
74 |
96 |
3.20 |
202 |
3 |
1.00 |
10.2 |
12 |
Comp.Ex.6 |
54 |
57 |
1.1 |
2.50 |
2.75 |
65 |
74 |
96 |
3.30 |
202 |
3 |
0.83 |
9.1 |
12 |
Comp.Ex.6 |
54 |
57 |
1.1 |
2.73 |
3.00 |
65 |
74 |
96 |
3.10 |
202 |
3 |
0.97 |
9.3 |
12 |
Comp.Ex.7 |
54 |
57 |
1.1 |
2.45 |
2.70 |
65 |
74 |
96 |
3.10 |
202 |
3 |
0.87 |
8.4 |
12 |
Comp.Ex.8 |
54 |
57 |
1.1 |
2.68 |
2.95 |
65 |
74 |
96 |
3.40 |
202 |
3 |
0.87 |
10.0 |
12 |
Comp.Ex.9 |
54 |
57 |
1.1 |
2.73 |
3.00 |
65 |
74 |
96 |
2.80 |
202 |
3 |
1.07 |
8.4 |
12 |
Comp.Ex.10 |
85 |
70 |
2.1 |
1.60 |
3.36 |
130 |
130 |
130 |
4.00 |
210 |
5 |
0.84 |
13.4 |
15 |
Comp.Ex.11 |
72 |
75 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Comp.Ex.12 |
52 |
56 |
1.1 |
2.59 |
2.85 |
55 |
58 |
82 |
3.30 |
202 |
3 |
0.86 |
9.4 |
12 |
Comp.Ex.13 |
72 |
75 |
1.1 |
2.41 |
2.65 |
65 |
74 |
96 |
3.15 |
202 |
3 |
0.84 |
8.4 |
12 |
Comp.Ex.14 |
54 |
57 |
1.1 |
2.59 |
2.85 |
55 |
58 |
82 |
3.40 |
202 |
3 |
0.84 |
9.7 |
12 |
Comp.Ex.15 |
46 |
49 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.40 |
202 |
3 |
0.84 |
9.7 |
12 |
Comp.Ex.16 |
54 |
57 |
1.1 |
2.41 |
2.65 |
82 |
74 |
96 |
3.15 |
202 |
3 |
0.84 |
8.4 |
12 |
[0126] In Tables 1 to 3, each draw ratio indicates the draw ratio based on a value of 1.
In addition, each heat treatment temperature is in units of "°C", relaxation rate
is in units of "%", and target thicknesses are indicated in "µm".
Test Example 1
[0127] Properties were evaluated for the polyamide-based films and laminates obtained in
Examples 1 to 28 and Comparative Examples 1 to 16. The evaluation results are shown
in Tables 4 to 9. Furthermore, the methods used to measure and evaluate each property
are indicated below.
(1) Stress of Polyamide-Based Film in Four Directions at 5% Elongation and 15% Elongation
[0128] The stress of the polyamide-based films in four directions at 5% elongation and 15%
elongation was measured and calculated according to the previously explained method
after having designated MD for the reference direction (0 degree direction).
[0129] The sample films used for measurement were sampled at a location in or near the center
of the wound width and corresponding to half the wound amount in the resulting polyamide-based
film wound into a roll.
(2) Average Thickness and Standard Deviation of Polyamide-Based Film
[0130] The average thickness and standard deviation of the polyamide-based films were respectively
measured and calculated according to the previously described methods. Furthermore,
the following three types of samples were used for the sample films used for measurement.
[0131] In the resulting polyamide-based films wound into a roll, a) sample film sampled
at a location near the center of the wound width and corresponding to half the wound
amount was designated as "A", b) sample film sampled at a location near the right
end of the wound width and corresponding to half the wound amount was designated as
"B", and c) sample film near the left end of the wound width and corresponding to
close to the end of winding was designated as "C".
(3) Boiling Water Shrinkage, Modulus of Elasticity and Relative Viscosity of Polyamide-Based
Film
[0132] The boiling water shrinkage, modulus of elasticity and relative viscosity of the
polyamide-based films were measured according to the previously indicated methods.
Furthermore, the sample films used for measurement were sampled at a location in or
near the center of the wound width and corresponding to half the wound amount in the
resulting polyamide-based films wound into a roll.
(4) Thickness of Primer Layer (Anchor Coat (AC) Layer)
[0133] The resulting polyamide-based films were embedded in epoxy resin followed by sampling
sections cut to a thickness of 100 nm with a freezing ultra-microtome. The sections
were cut at a temperature of -120°C at a cutting speed of 0.4 mm/min. The sampled
sections were subjected to gas-phase dyeing for 1 hour with RuO
4 solution followed by measurement of primer layer thickness at an accelerating voltage
of 100 kV by transmission measurement using a transmission electron microscope (TEM,
JEOL Ltd., JEM-1230). At this time, five arbitrary locations were selected for measurement
of primer layer thickness and the average of the measured values at those five locations
was taken to be the thickness of the primer layer.
[0134] Furthermore, the sample films used for measurement were sampled at a location near
the center of the wound width and corresponding to half the wound amount in the resulting
polyamide-based films wound into a roll.
(5) Laminate Moldability and Wet heat Resistance
1) Draw Depth (Erichsen Test)
[0135] A steel ball punch was pressed into the resulting laminates to a prescribed depth
followed by determination of Erichsen values using an Erichsen tester (Yasuda Seiki
Seisakusho Ltd., No. 5755) based on JIS Z 2247. Erichsen values were measured at 0.5
mm intervals. When the laminate has an Erichsen value of 5 mm or more, the laminate
was judged to be preferable. In particular, the laminate was judged to be more preferable
for deep drawing molding in the case of an Erichsen value of 8 mm or more.
2) Wet heat Resistance
[0136] The resulting laminates were subjected to an Erichsen test in the same manner as
1) above using a high-temperature, highpressure cooking and sterilizing device (Hisaka
Works Ltd., RCS-60SPXTG) after treating for 30 minutes at 120°C and 1.8 kg/cm
2 in order to evaluate molding stability under high temperature and high humidity conditions.
At this time, a steel ball punch was pressed into the laminates of the examples to
a location at which the Erichsen value became 8 mm, or was pressed into the laminates
of the comparative examples to a location at which the Erichsen value became 5 mm.
In this case, the laminates were visually examined for the occurrence of delamination
and the occurrence of breakage of the polyamide-based film or metal foil that composes
the laminates.
[0137] Those laminates in which there was no occurrence whatsoever of delamination or breakage
of the polyamide-based film or metal foil were indicated with an "○", those laminates
in which there was partial occurrence of delamination but no occurrence of breakage
of the polyamide-based film or metal-foil were indicated with a "Δ", and those laminates
in which delamination or breakage of the polyamide-based film or metal foil occurred
were indicated with an "X".
[Table 4]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Ex.1 |
11.9 |
0.128 |
11.9 |
0.130 |
12.0 |
0.132 |
-- |
Ex.2 |
12.1 |
0.130 |
12.0 |
0.133 |
12.0 |
0.127 |
-- |
Ex.3 |
12.0 |
0.124 |
12.1 |
0.125 |
11.9 |
0.126 |
-- |
Ex.4 |
12.1 |
0.130 |
12.0 |
0.132 |
12.0 |
0.130 |
-- |
Ex.5 |
11.8 |
0.126 |
11.9 |
0.125 |
12.1 |
0.128 |
-- |
Ex.6 |
11.9 |
0.132 |
11.8 |
0.132 |
12.0 |
0.130 |
-- |
Ex.7 |
Used polyamide-based film of Example 1 |
Ex.8 |
14.9 |
0.148 |
15.0 |
0.146 |
14.8 |
0.150 |
-- |
Ex.9 |
9.8 |
0.120 |
9.9 |
0.122 |
10.1 |
0.120 |
-- |
Ex.10 |
10.0 |
0.118 |
10.0 |
0.119 |
9.9 |
0.120 |
-- |
Ex.11 |
9.9 |
0.122 |
10.0 |
0.120 |
10.0 |
0.124 |
-- |
Ex.12 |
10.1 |
0.116 |
9.9 |
0.118 |
10.0 |
0.114 |
-- |
Ex.13 |
10.0 |
0.118 |
10.2 |
0.118 |
9.9 |
0.118 |
-- |
Ex.14 |
9.9 |
0.120 |
10.0 |
0.121 |
10.1 |
0.119 |
-- |
[Table 5]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Ex.15 |
24.8 |
0.158 |
25.0 |
0.156 |
24.8 |
0.157 |
-- |
Ex.16 |
8.2 |
0.120 |
8.1 |
0.118 |
8.1 |
0.119 |
-- |
Ex.17 |
11.9 |
0.169 |
12.0 |
0.172 |
12.0 |
0.179 |
-- |
Ex.18 |
15.0 |
0.140 |
15.1 |
0.136 |
15.1 |
0.138 |
-- |
Ex.19 |
14.8 |
0.136 |
14.9 |
0.138 |
14.9 |
0.137 |
-- |
Ex.20 |
11.9 |
0.120 |
11.8 |
0.118 |
12.0 |
0.119 |
-- |
Ex.21 |
12.0 |
0.118 |
12.1 |
0.120 |
12.1 |
0.119 |
-- |
Ex.22 |
12.1 |
0.126 |
12.1 |
0.130 |
12.1 |
0.128 |
-- |
Ex.23 |
12.0 |
0.130 |
12.0 |
0.125 |
12.0 |
0.126 |
-- |
Ex.24 |
25.0 |
0.157 |
25.1 |
0.156 |
25.0 |
0.154 |
-- |
Ex.25 |
24.9 |
0.155 |
25.0 |
0.155 |
24.8 |
0.154 |
-- |
Ex.26 |
11.8 |
0.162 |
11.9 |
0.163 |
11.8 |
0.163 |
-- |
Ex.27 |
12.1 |
0.164 |
12.0 |
0.165 |
12.1 |
0.163 |
-- |
Ex.28 |
12.1 |
0.168 |
12.1 |
0.169 |
12.0 |
0.168 |
-- |
[Table 6]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Comp.Ex.1 |
12.1 |
0.274 |
11.9 |
0.280 |
11.9 |
0.284 |
-- |
Comp.Ex.2 |
12.0 |
0.229 |
11.8 |
0.234 |
12.0 |
0.236 |
-- |
Comp.Ex.3 |
12.1 |
0.333 |
12.0 |
0.330 |
11.8 |
0.328 |
-- |
Comp.Ex.4 |
11.8 |
0.243 |
11.9 |
0.250 |
11.9 |
0.252 |
-- |
Comp.Ex.5 |
12.0 |
0.249 |
12.0 |
0.252 |
12.0 |
0.259 |
-- |
Comp.Ex.6 |
11.9 |
0.244 |
11.9 |
0.246 |
12.1 |
0.240 |
-- |
Comp.Ex.7 |
11.9 |
0.255 |
12.0 |
0.265 |
12.0 |
0.262 |
-- |
Comp.Ex.8 |
12.0 |
0.239 |
12.2 |
0.231 |
12.1 |
0.245 |
-- |
Comp.Ex.9 |
12.0 |
0.298 |
12.1 |
0.305 |
12.1 |
0.300 |
-- |
Comp.Ex.10 |
15.2 |
0.411 |
15.0 |
0.420 |
15.0 |
0.413 |
-- |
Comp.Ex.11 |
11.9 |
0.445 |
12.0 |
0.450 |
12.0 |
0.456 |
-- |
Comp.Ex.12 |
12.1 |
0.515 |
12.1 |
0.527 |
12.1 |
0.526 |
-- |
Comp.Ex.13 |
12.2 |
0.510 |
12.1 |
0.515 |
12.3 |
0.512 |
-- |
Comp.Ex.14 |
12.0 |
0.406 |
12.0 |
0.411 |
12.1 |
0.408 |
-- |
Comp.Ex.15 |
11.9 |
0.453 |
11.8 |
0.450 |
12.0 |
0.450 |
-- |
Comp.Ex.16 |
11.9 |
0.479 |
11.9 |
0.482 |
12.0 |
0.480 |
-- |
[Table 7]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Ex.1 |
53.8 |
53.0 |
55.4 |
69.8 |
16.8 |
95.6 |
91.8 |
94.2 |
112.5 |
20.7 |
2.6 |
3.2 |
2.2 |
2.1 |
2.98 |
10.0 |
Δ |
Ex.2 |
66.4 |
54.8 |
55.9 |
78.4 |
23.6 |
94.0 |
82.5 |
92.8 |
112.3 |
29.8 |
3.6 |
4.2 |
2.3 |
2.2 |
3.00 |
8.4 |
Δ |
Ex.3 |
71.8 |
56.0 |
54.2 |
72.3 |
18.1 |
90.5 |
95.5 |
100.0 |
112.5 |
22.0 |
3.8 |
4.3 |
2.2 |
1.8 |
2.97 |
9.5 |
Δ |
Ex.4 |
70.5 |
51.3 |
53.8 |
72.1 |
20.8 |
94.0 |
86.0 |
92.8 |
113.5 |
27.5 |
3.6 |
4.1 |
2.4 |
2.3 |
2.96 |
8.7 |
Δ |
Ex.5 |
68.4 |
59.0 |
82.9 |
65.7 |
23.9 |
116.5 |
100.8 |
112.8 |
129.2 |
28.4 |
4.2 |
4.8 |
2.1 |
1.8 |
2.98 |
8.3 |
Δ |
Ex.6 |
69.8 |
56.9 |
53.4 |
72.8 |
19.4 |
90.5 |
83.4 |
91.0 |
106.5 |
23.1 |
2.4 |
2.6 |
2.0 |
1.7 |
3.01 |
9.6 |
Δ |
Ex.7 |
Used Polyamide-based Film of Example 1 |
2.98 |
8.5 |
Δ |
Ex.8 |
54.9 |
52.8 |
53.0 |
68.7 |
15.9 |
95.6 |
91.8 |
94.2 |
112.5 |
20.7 |
2.7 |
3.1 |
2.2 |
2.0 |
2.96 |
9.0 |
Δ |
Ex.9 |
63.2 |
54.8 |
52.9 |
69.7 |
16.8 |
89.5 |
82.1 |
90.0 |
101.9 |
19.8 |
2.8 |
3.4 |
2.4 |
2.1 |
2.97 |
9.9 |
Δ |
Ex.10 |
68.4 |
57.4 |
54.6 |
79.5 |
24.9 |
93.7 |
81.2 |
94.8 |
108.1 |
26.9 |
3.9 |
4.4 |
2.4 |
2.3 |
3.00 |
8.1 |
Δ |
Ex.11 |
54.6 |
52.6 |
50.0 |
68.3 |
18.3 |
89.6 |
94.5 |
101.7 |
108.1 |
18.5 |
3.9 |
4.6 |
2.1 |
1.8 |
2.96 |
9.8 |
Δ |
Ex.12 |
67.1 |
52.8 |
54.0 |
73.9 |
21.1 |
97.4 |
83.3 |
91.5 |
109.6 |
26.3 |
3.6 |
4.2 |
2.4 |
2.3 |
2.97 |
8.6 |
Δ |
Ex.13 |
66.4 |
55.9 |
80.7 |
66.2 |
24.8 |
117.2 |
96.3 |
107.8 |
125.4 |
29.1 |
4.5 |
5.2 |
2.0 |
1.8 |
3.00 |
7.8 |
Δ |
Ex.14 |
64.0 |
53.5 |
49.4 |
70.2 |
20.8 |
88.4 |
81.8 |
89.2 |
103.1 |
21.3 |
2.1 |
2.7 |
2.0 |
1.8 |
2.99 |
8.9 |
Δ |
[Table 8]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Ex.15 |
56.4 |
54.8 |
53.2 |
71.0 |
17.8 |
98.8 |
96.9 |
92.0 |
113.2 |
21.2 |
2.8 |
3.4 |
2.3 |
2.1 |
2.98 |
9.8 |
Δ |
Ex.16 |
56.4 |
52.1 |
54.2 |
67.4 |
15.3 |
89.5 |
80.2 |
93.0 |
101.1 |
20.9 |
2.9 |
3.5 |
2.2 |
2.1 |
2.98 |
9.6 |
Δ |
Ex.17 |
56.8 |
51.5 |
58.9 |
75.6 |
24.1 |
92.7 |
80.0 |
94.9 |
109.9 |
29.9 |
2.5 |
3.1 |
2.2 |
2.1 |
2.96 |
7.6 |
Δ |
Ex.18 |
55.4 |
51.3 |
56.7 |
68.4 |
17.1 |
89.6 |
85.2 |
90.1 |
108.4 |
23.2 |
3.7 |
4.2 |
2.1 |
2.2 |
3.00 |
9.4 |
Δ |
Ex.19 |
69.8 |
52.3 |
54.1 |
71.3 |
19.0 |
92.3 |
96.0 |
98.9 |
115.6 |
23.3 |
2.8 |
3.4 |
2.2 |
2.1 |
3.02 |
9.6 |
Δ |
Ex.20 |
55.1 |
54.6 |
53.2 |
68.9 |
15.7 |
93.5 |
82.0 |
94.3 |
104.9 |
22.9 |
3.8 |
4.3 |
2.3 |
2.0 |
2.99 |
9.0 |
Δ |
Ex.21 |
68.7 |
54.1 |
53.9 |
72.3 |
18.4 |
91.2 |
97.0 |
95.0 |
110.9 |
19.7 |
2.5 |
3.1 |
2.3 |
2.1 |
2.98 |
9.4 |
Δ |
Ex.22 |
70.1 |
56.3 |
51.0 |
74.3 |
23.3 |
93.5 |
84.9 |
98.1 |
105.1 |
20.2 |
3.7 |
4.2 |
2.3 |
2.0 |
2.98 |
8.2 |
Δ |
Ex.23 |
71.3 |
54.9 |
52.8 |
70.5 |
18.5 |
94.6 |
86.2 |
98.1 |
110.1 |
23.9 |
3.4 |
4.0 |
2.2 |
2.3 |
3.00 |
9.5 |
Δ |
Ex.24 |
56.9 |
74.0 |
76.2 |
58.6 |
19.3 |
87.2 |
107.9 |
117.8 |
89.4 |
30.6 |
3.0 |
3.6 |
2.5 |
2.2 |
3.01 |
8.4 |
Δ |
Ex.25 |
58.5 |
76.5 |
79.6 |
60.7 |
21.1 |
89.4 |
112.7 |
120.1 |
90.8 |
30.7 |
2.8 |
3.3 |
2.4 |
2.1 |
3.00 |
8.2 |
Δ |
Ex.26 |
52.4 |
59.6 |
60.1 |
77.9 |
25.5 |
89.3 |
91.8 |
94.2 |
119.7 |
30.4 |
2.2 |
2.4 |
1.8 |
1.4 |
2.99 |
6.9 |
Δ |
Ex.27 |
50.0 |
69.5 |
75.8 |
65.9 |
25.8 |
85.1 |
110.7 |
116.2 |
98.7 |
31.1 |
1.9 |
2.6 |
1.4 |
1.8 |
2.98 |
6.8 |
Δ |
Ex.28 |
49.5 |
74.5 |
75.9 |
56.4 |
26.4 |
84.9 |
106.8 |
116.5 |
92.4 |
31.6 |
1.9 |
2.3 |
1.3 |
1.4 |
2.99 |
6.5 |
Δ |
[Table 9]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Comp.Ex.1 |
56.9 |
49.6 |
55.5 |
87.8 |
38.2 |
98.8 |
89.4 |
92.1 |
130.9 |
41.5 |
4.9 |
5.4 |
1.4 |
2.5 |
3.00 |
4.4 |
X |
Comp.Ex.2 |
93.6 |
52.2 |
56.8 |
60.0 |
41.4 |
138.4 |
87.1 |
95.5 |
98.2 |
51.3 |
2.7 |
3.5 |
3.2 |
2.6 |
3.02 |
2.5 |
X |
Comp.Ex.3 |
56.6 |
50.4 |
89.9 |
54.1 |
39.5 |
101.1 |
94.5 |
140.0 |
96.2 |
45.5 |
5.9 |
6.4 |
1.4 |
2.6 |
2.97 |
3.6 |
X |
Comp.Ex.4 |
60.5 |
54.2 |
58.4 |
91.6 |
37.4 |
106.9 |
97.9 |
93.4 |
134.0 |
40.6 |
5.6 |
6.2 |
3.1 |
1.4 |
2.98 |
3.5 |
X |
Comp.Ex.5 |
74.1 |
47.9 |
52.4 |
88.1 |
40.2 |
118.2 |
89.4 |
91.3 |
136.7 |
47.3 |
5.0 |
5.4 |
2.5 |
2.8 |
2.97 |
3.1 |
X |
Comp.Ex.6 |
62.4 |
52.0 |
55.1 |
91.8 |
39.8 |
111.2 |
91.5 |
94.8 |
135.1 |
43.6 |
5.2 |
5.6 |
3.2 |
1.4 |
3.00 |
3.6 |
X |
Comp.Ex.7 |
80.0 |
49.3 |
51.7 |
83.1 |
33.8 |
123.9 |
96.8 |
99.9 |
140.7 |
43.9 |
5.9 |
6.4 |
1.3 |
1.5 |
3.01 |
4.1 |
X |
Comp.Ex.8 |
88.6 |
61.9 |
53.0 |
61.8 |
35.6 |
139.0 |
102.7 |
92.5 |
111.1 |
46.5 |
5.4 |
6.0 |
3.2 |
1.4 |
2.99 |
4.0 |
X |
Comp.Ex.9 |
46.9 |
54.0 |
89.9 |
55.2 |
43.0 |
88.4 |
95.6 |
136.0 |
90.8 |
47.6 |
6.1 |
6.5 |
2.5 |
1.4 |
3.02 |
3.5 |
X |
Comp.Ex.10 |
92.3 |
71.9 |
105.1 |
117.5 |
45.6 |
110.6 |
89.2 |
132.6 |
156.2 |
67.0 |
1.4 |
2.4 |
3.3 |
1.9 |
2.98 |
2.4 |
X |
Comp.Ex.11 |
52.1 |
89.7 |
88.6 |
56.4 |
37.6 |
84.0 |
123.3 |
122.8 |
90.4 |
39.3 |
2.6 |
3.2 |
1.4 |
2.0 |
2.98 |
2.6 |
X |
Comp.Ex.12 |
53.4 |
76.8 |
90.8 |
58.1 |
37.4 |
90.9 |
92.1 |
120.0 |
131.4 |
40.5 |
2.8 |
3.4 |
3.2 |
2.8 |
2.99 |
2.0 |
X |
Comp.Ex.13 |
54.9 |
95.4 |
101.5 |
69.8 |
46.6 |
84.7 |
129.9 |
127.4 |
94.0 |
45.2 |
5.4 |
5.2 |
1.2 |
2.6 |
3.00 |
2.6 |
X |
Comp.Ex.14 |
73.8 |
53.7 |
61.0 |
94.0 |
40.3 |
87.4 |
83.4 |
119.1 |
124.1 |
40.7 |
2.9 |
3.6 |
3.3 |
2.6 |
3.01 |
2.9 |
X |
Comp.Ex.15 |
80.5 |
52.9 |
56.7 |
93.4 |
40.5 |
90.4 |
81.7 |
121.7 |
125.6 |
43.9 |
2.9 |
3.6 |
3.4 |
2.7 |
3.00 |
2.1 |
X |
Comp.Ex.16 |
50.2 |
85.7 |
92.8 |
86.9 |
42.6 |
78.5 |
110.0 |
124.9 |
90.1 |
46.4 |
5.4 |
5.2 |
3.2 |
2.6 |
2.98 |
2.4 |
X |
[0138] In Tables 4 to 9, average thickness is in units of "µm", AC layer thickness is in
units of "µm", stress is in units of "MPa", boiling water shrinkage is in units of
"%", modulus of elasticity is units of "%", and draw depth is in units of "mm".
[0139] As is clear from these results, in Examples 1 to 28, since the draw ratios of the
resulting polyamide-based films were within a specified range, the difference between
the maximum value and minimum value of stress at 5% elongation in the 0 degree direction
(MD), 45 degree direction, 90 degree direction (TD) and 135 degree direction in uniaxial
tensile tests of the resulting polyamide-based films was 35 MPa or less while the
difference between the maximum value and minimum value at 15% elongation was 40 MPa
or less. Laminates obtained using these polyamide-based films demonstrated high Erichsen
values and had uniform ductility in all directions during cold forming. In other words,
the polyamide-based films of each of Examples exhibited superior moldability without
the occurrence of problems such as breakage of the aluminum foil, delamination or
the formation of pinholes.
[0140] On the other hand, in Comparative Examples 1 to 16, since the draw ratios of the
polyamide-based films did not satisfy a specific range, the difference between the
maximum value and minimum value of stress at 5% elongation in the 0 degree direction
(MD), 45 degree direction, 90 degree direction (TD) and 135 degree direction in uniaxial
tension tests of the resulting polyamide-based films did not satisfy the requirement
of 35 MPa or less, and the difference between the maximum value and minimum value
at 15% elongation did not satisfy the requirement of 45 MPa or less. Consequently,
-laminates obtained using these polyamide-based films of the comparative examples
demonstrate low Erichsen values and have inferior moldability as a result of failing
to demonstrate uniform ductility in all directions during cold forming.
Example 29
(1) Production of Polyamide-Based Film
[0141] An unstretched sheet was produced by using a Polyamide 6 resin (Unitika Ltd., A1030BRF,
relative viscosity: 3.1, monomer content: 1.0% or less) and Silica-containing Nylon
6 resin that contains 6% by mass of silica (Unitika Ltd., A1030QW, relative viscosity:
2.7, monomer content: 1.0% or less) as raw materials, melting and kneading in an extruding
machine at a component ratio of A1030BRF/Silica-containing Nylon resin of 98.7/1.3
(mass ratio), supplying to a T-die and then discharging in the form of a sheet. The
resulting sheet was then wound around a metal drum adjusted to a temperature of 20°C
followed by cooling and taking up into a roll. At this time, the feed rate of the
polyamide resin was adjusted so that the thickness of the polyamide-based film obtained
after stretching was 15 µm.
[0142] The resulting unstretched sheet was subjected to a stretching step by successive
biaxial stretching. More specifically, stretching was carried out by a method involving
stretching in the MD using rollers followed by stretching in the TD using a tenter.
[0143] First, the unstretched sheet was stretched in the MD to a total draw ratio in the
MD of 2.85 times by passing the above-mentioned sheet over a plurality of rollers.
At this time, stretching was carried out in two stages, the draw ratio in the first
stage was 1.1 times, the draw ratio in the second stage was 2.59 times, and the total
draw ratio (MD1 × MD2) was 1.1 × 2.59 = 2.85 times. As to heating conditions, a temperature
gradient along the receiving direction of the film was formed so that the temperature
(T1) at the start in the traveling direction was 58°C and the temperature (T2) at
the end was 61°C in the MD stretching. At this time, transit time (heating time) of
the film from the start (entrance) to the end (exit) of the film in the traveling
direction was about 3 seconds.
[0144] After that, an aqueous polyurethane dispersion was coated onto one side of the film
to a coating thickness after stretching of 0.03 µm to 0.08 µm with a gravure coater
in order to form a primer layer following stretching in the MD. This was followed
by stretching in the TD. As the above-mentioned aqueous dispersion,' an aqueous coating
agent prepared by mixing 7 parts by mass of a tri(methoxymethyl)melamine resin (DIC
Corp., Beckamine APM, Tts = 150°C) to 100 parts by mass of an anionic water-dispersible
polyurethane resin (DIC Corp., Hydran KU400SF, Tmf = approx. 0°C, Tsf = 80°C) was
used.
[0145] Next, stretching in the TD was carried out using a tenter as shown in Fig. 3. First,
the film was stretched at a draw ratio of 3.2 times in the TD in the stretching zone
while preheating to a temperature of 70°C in the preheating zone (preheating section).
At this time, a temperature gradient along the receiving direction of the film was
applied to the stretching zone (stretching section) so that the temperature at the
start (T1) of the film in the traveling direction was 78°C and the temperature at
the end (T2) was 100°C. At this time, transit time (heating time) of the film from
the start (entrance) to the end (exit) of the film in the traveling direction in the
stretching zone was about 3 seconds.
[0146] After having passed through the stretching zone, the film was subjected to relaxation
heat treatment in the relaxation heat treatment zone (heat treatment section) under
conditions of a temperature of 202°C and relaxation rate of 3%. A biaxially stretched
polyamide-based film (wound length: 2000 m) was obtained by continuously producing
1000 m or more in this manner. The resulting film was taken up into the form of a
roll.
(2) Laminate Fabrication
[0147] A laminate (formed of the polyamide-based film/aluminum foil/sealant film) was fabricated
in the same manner as Example 1 with the exception of using the biaxially,stretched
polyamide-based film obtained in (1) above and laminating the aluminum foil on the
surface of the primer layer using a two-pack type polyurethane-based adhesive.
Examples 30-59 and Comparative Examples 17-36
[0148] Polyamide-based films were obtained using the same method as Example 29 with the
exception of changing the production conditions and target thickness of the stretched
polyamide-based film to those shown in Tables 10 to 12. Laminates were then fabricated
in the same manner as Example 29 using the resulting polyamide-based films. However,
the changes made in Examples 35, 43 and 51 are described in detail below.
(1) Example 35
[0149] After coating a two-component polyurethane-based adhesive (Toyo-Morton, Ltd., TM-K55/CAT-10L)
onto the side of the polyamide-based film on which the aluminum foil was not laminated
in the laminate obtained in Example 29 to a coated amount of 5 g/m
2, the coated film was dried for 10 seconds at 80°C. A PET film (Unitika Ltd., Emblet
PET-12, thickness: 12 µm) was laminated onto the adhesive-coated side thereof to fabricate
a laminate (formed of the PET film/polyamide-based film/aluminum foil/sealant film).
(2) Example 43
[0150] After coating a two-component polyurethane-based adhesive (Toyo-Morton, Ltd., TM-K55/CAT-10L)
onto the side of the polyamide-based film on which the aluminum foil was not laminated
in the laminate obtained in Example 36 to a coated amount of 5 g/m
2, the coated film was dried for 10 seconds at 80°C. A PET film (Unitika Ltd., Emblet
PET-12, thickness: 12 µm) was laminated onto the adhesive-coated side thereof to fabricate
a laminate (formed of the PET film, polyamide-based film, aluminum foil and sealant
film).
(3) Example 51
[0151] A polyamide-based film was obtained using the same method as Example 29 with the
exception of using a composition containing Polyamide 6 resin (Unitika Ltd., A1030BRF),
Polyamide 66 resin (Unitika Ltd., A226) and Nylon 6 resin containing 6% by mass of
silica at a component ratio of A1030BRF/A226/silica-containing nylon resin of 89.0/9.7/1.3
(mass ratio) as raw material in the production of the polyamide-based film indicated
in Example 29. A laminate was fabricated in the same manner as Example 29 using the
resulting polyamide-based film.
[Table 10]
|
MD Direction |
TD Direction |
MD/TD |
MD×TD |
Target Thickness |
Preheating section |
Stretching Section |
Heat Treatment Section |
Heat Treatment Temp. |
Draw Ratio |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
1st stage MD1 |
2nd Stage MD2 |
Total draw ratio MD1×MD2 |
T1 |
T2 |
Ex.29 |
58 |
61 |
1.1 |
2.59 |
2.85 |
70 |
78 |
100 |
3.20 |
202 |
3 |
0.89 |
9.1 |
15 |
Ex. 30 |
58 |
61 |
1.1 |
2.59 |
2.85 |
70 |
78 |
100 |
3.30 |
202 |
3 |
0.86 |
9.4 |
15 |
Ex.31 |
58 |
61 |
1.1 |
2.59 |
2.85 |
70 |
78 |
100 |
3.05 |
202 |
3 |
0.93 |
8.7 |
15 |
Ex.32 |
58 |
61 |
1.1 |
2.68 |
2.95 |
70 |
78 |
100 |
3.20 |
202 |
3 |
0.92 |
9.4 |
15 |
Ex.33 |
58 |
61 |
1.1 |
2.48 |
2.73 |
70 |
78 |
100 |
3.20 |
202 |
3 |
0.85 |
8.7 |
15 |
Ex.34 |
58 |
61 |
1.1 |
2.59 |
2.85 |
70 |
78 |
100 |
3.20 |
213 |
3 |
0.89 |
9.1 |
15 |
Ex.35 |
Used Poly amide-Based Resin of Example 29 |
Ex.36 |
60 |
64 |
1.1 |
2.59 |
2.85 |
78 |
84 |
104 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
Ex.37 |
54 |
57 |
1.2 |
2.38 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.38 |
54 |
57 |
1.2 |
2.38 |
2.85 |
65 |
74 |
96 |
3.30 |
202 |
3 |
0.86 |
9.4 |
12 |
Ex.39 |
54 |
57 |
1.2 |
2.38 |
2.85 |
65 |
74 |
96 |
3.05 |
202 |
3 |
0.93 |
8.7 |
12 |
Ex.40 |
54 |
57 |
1.2 |
2.46 |
2.95 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.92 |
9.4 |
12 |
Ex.41 |
54 |
57 |
1.2 |
2.28 |
2.73 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.85 |
8.7 |
12 |
Ex.42 |
54 |
57 |
1.2 |
2.38 |
2.85 |
65 |
74 |
96 |
3.20 |
213 |
3 |
0.89 |
9.1 |
12 |
Ex.43 |
Used Polyamide-Based Resin of Example 36 |
[Table 11]
|
MD Direction |
TD Direction |
MD/TD |
MD×TD |
Target Thickness |
Preheating section |
Stretching Section |
Heat Treatment Section |
Heat Treatment Temp. |
Draw Ratio |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
1st stage MD1 |
2nd Stage MD2 |
Total draw ratio MD1×MD2 |
T1 |
T2 |
Ex.44 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.20 |
202 |
3 |
0.89 |
9.1 |
10 |
Ex.45 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.30 |
202 |
3 |
0.86 |
9.4 |
10 |
Ex.46 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.05 |
202 |
3 |
0.93 |
8.7 |
10 |
Ex.47 |
52 |
55 |
1.2 |
2.38 |
2.95 |
64 |
72 |
95 |
3.20 |
202 |
3 |
0.92 |
9.4 |
10 |
Ex.48 |
52 |
55 |
1.2 |
2.38 |
2.73 |
64 |
72 |
95 |
3.20 |
202 |
2 |
0.85 |
8.7 |
10 |
Ex.49 |
52 |
55 |
1.2 |
2.38 |
2.85 |
64 |
72 |
95 |
3.20 |
213 |
4 |
0.89 |
9.1 |
10 |
Ex.50 |
50 |
54 |
1.1 |
2.59 |
2.85 |
63 |
70 |
94 |
3.20 |
202 |
5 |
0.89 |
9.1 |
8 |
Ex.51 |
60 |
64 |
1.1 |
2.59 |
2.85 |
80 |
90 |
110 |
3.20 |
202 |
5 |
0.89 |
9.1 |
12 |
Ex.52 |
59 |
63 |
1.05 |
2.71 |
2.85 |
70 |
78 |
100 |
3.20 |
202 |
2 |
0.89 |
9.1 |
15 |
Ex.53 |
58 |
61 |
1.1 |
2.59 |
2.85 |
69 |
76 |
102 |
3.20 |
202 |
2 |
0.89 |
9.1 |
15 |
Ex.54 |
54 |
63 |
1.05 |
2.71 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.55 |
55 |
58 |
1.2 |
2.38 |
2.85 |
65 |
73 |
98 |
3.20 |
202 |
3 |
0.89 |
9.1 |
12 |
Ex.56 |
54 |
63 |
1.05 |
2.81 |
2.95 |
65 |
74 |
96 |
3.20 |
202 |
4 |
0.92 |
9.4 |
12 |
Ex.57 |
55 |
58 |
1.2 |
2.46 |
2.95 |
65 |
73 |
98 |
3.20 |
202 |
4 |
0.92 |
9.4 |
12 |
Ex.58 |
70 |
74 |
1.1 |
2.59 |
2.85 |
78 |
84 |
104 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
Ex.59 |
60 |
64 |
1.1 |
2.59 |
2.85 |
78 |
90 |
115 |
3.20 |
202 |
4 |
0.89 |
9.1 |
25 |
[Table 12]
|
MD Direction |
TD Direction |
MD/TD |
MD×TD |
Target Thickness |
Preheating section |
Stretching Section |
Heat Treatment Section |
Heat Treatment Temp. |
Draw Ratio |
Heat Treatment Temp. |
Heat Treatment Temp. |
Draw Ratio TD |
Heat Treatment Temp. |
Relaxation Rate |
T1 |
T2 |
1st stage MD1 |
2nd Stage MD2 |
Total draw ratio MD1×MD2 |
T1 |
T2 |
Comp.Ex.17 |
58 |
61 |
1.1 |
2.33 |
2.56 |
70 |
78 |
100 |
3.20 |
202 |
3 |
0.8 |
8.2 |
15 |
Comp.Ex.18 |
58 |
61 |
1.1 |
2.55 |
2.80 |
70 |
78 |
100 |
3.60 |
202 |
3 |
0.78 |
10.1 |
15 |
Comp.Ex.19 |
58 |
61 |
1.2 |
2.33 |
2.80 |
70 |
78 |
100 |
2.80 |
202 |
3 |
1.00 |
7.8 |
15 |
Comp.Ex.20 |
58 |
61 |
1.2 |
2.67 |
3.20 |
70 |
78 |
100 |
3.20 |
202 |
3 |
1.00 |
10.2 |
15 |
Comp.Ex.21 |
58 |
61 |
1.2 |
2.29 |
2.75 |
70 |
78 |
100 |
3.30 |
202 |
3 |
0.83 |
9.1 |
15 |
Comp.Ex.22 |
58 |
61 |
1.2 |
2.50 |
3.00 |
70 |
78 |
100 |
3.10 |
202 |
3 |
0.97 |
9.3 |
15 |
Comp.Ex.23 |
58 |
61 |
1.2 |
2.25 |
2.70 |
70 |
78 |
100 |
3.10 |
202 |
3 |
0.87 |
8.4 |
15 |
Comp.Ex.24 |
58 |
61 |
1.2 |
2.46 |
2.95 |
70 |
78 |
100 |
3.40 |
202 |
3 |
0.87 |
10.0 |
15 |
Comp.Ex.25 |
58 |
61 |
1.2 |
2.50 |
3.00 |
70 |
78 |
100 |
2.80 |
202 |
3 |
1.07 |
8.4 |
15 |
Comp.Ex.26 |
58 |
61 |
1.2 |
2.13 |
2.56 |
70 |
78 |
100 |
3.20 |
202 |
3 |
0.8 |
8.2 |
12 |
Comp.Ex.27 |
58 |
61 |
1.2 |
2.33 |
2.80 |
70 |
78 |
100 |
3.60 |
202 |
3 |
0.78 |
10.1 |
12 |
Comp.Ex.28 |
58 |
61 |
1.2 |
2.23 |
2.80 |
70 |
78 |
100 |
2.80 |
202 |
3 |
1.00 |
7.8 |
12 |
Comp.Ex.29 |
58 |
61 |
1.2 |
2.25 |
2.70 |
70 |
78 |
100 |
3.10 |
202 |
3 |
0.87 |
8.4 |
12 |
Comp.Ex.30 |
85 |
70 |
2.1 |
1.6 |
3.36 |
130 |
130 |
130 |
4.00 |
210 |
5 |
0.84 |
13.44 |
15 |
Comp.Ex.31 |
72 |
75 |
1.1 |
2.59 |
2.85 |
65 |
74 |
96 |
3.20 |
202 |
3 |
0.89 |
9.10 |
12 |
Comp.Ex.32 |
52 |
56 |
1.1 |
2.59 |
2.85 |
55 |
58 |
82 |
3.30 |
202 |
3 |
0.89 |
9.10 |
12 |
Comp.Ex.33 |
72 |
75 |
1.1 |
2.41 |
2.65 |
55 |
58 |
82 |
3.05 |
202 |
3 |
0.86 |
9.40 |
12 |
Comp.Ex.34 |
54 |
57 |
1.1 |
2.59 |
2.85 |
55 |
58 |
82 |
3.20 |
202 |
3 |
0.93 |
8.70 |
12 |
Comp.Ex.35 |
46 |
49 |
1.1 |
2.59 |
2.85 |
55 |
58 |
82 |
3.20 |
202 |
3 |
0.92 |
9.40 |
12 |
Comp.Ex.36 |
54 |
57 |
1.1 |
2.41 |
2.65 |
55 |
58 |
82 |
3.20 |
213 |
3 |
0.85 |
8.70 |
12 |
[0152] In Tables 10 to 12, each draw ratio indicates the draw ratio based on a value of
1. In addition, each heat treatment temperature is in units of "°C", relaxation rate
is in units of "%", and target thicknesses are indicated in "µm".
Test Example 2
[0153] Properties were evaluated for the polyamide-based films and laminates obtained in
Examples 29 to 59 and Comparative Examples 17 to 36. The evaluation results are shown
in Tables 13 to 18. Furthermore, the methods used to measure and evaluate each property
were the same as those used in Test Example 1.
[Table 13]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Ex.29 |
15.1 |
0.156 |
15.2 |
0.150 |
15.1 |
0.152 |
0.05 |
Ex.30 |
15.0 |
0.149 |
15.0 |
0.148 |
15.0 |
0.150 |
0.04 |
Ex.31 |
14.9 |
0.152 |
15.1 |
0.154 |
14.9 |
0.150 |
0.07 |
Ex.32 |
15.0 |
0.156 |
15.1 |
0.156 |
14.9 |
0.155 |
0.08 |
Ex.33 |
14.8 |
0.145 |
14.9 |
0.140 |
15.0 |
0.142 |
0.05 |
Ex.34 |
15.1 |
0.150 |
15.0 |
0.152 |
15.1 |
0.149 |
0.04 |
Ex.35 |
Used Polyamide-Based Film of Example 29 |
Ex.36 |
25.2 |
0.154 |
25.2 |
0.156 |
25.1 |
0.152 |
0.07 |
Ex.37 |
11.8 |
0.136 |
11.9 |
0.140 |
11.8 |
0.136 |
0.05 |
Ex.38 |
11.7 |
0.131 |
11.8 |
0.132 |
11.8 |
0.130 |
0.04 |
Ex.39 |
11.9 |
0.134 |
11.9 |
0.136 |
12.0 |
0.135 |
0.04 |
Ex.40 |
11.8 |
0.130 |
12.0 |
0.132 |
11.9 |
0.134 |
0.02 |
Ex.41 |
12.0 |
0.129 |
12.0 |
0.134 |
12.0 |
0.132 |
0.05 |
Ex.42 |
11.9 |
0.128 |
12.0 |
0.136 |
11.9 |
0.131 |
0.06 |
Ex.43 |
Used Polyamide-Based Film of Example 36 |
[Table 14]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Ex.44 |
9.8 |
0.119 |
10.0 |
0.118 |
9.9 |
0.123 |
0.02 |
Ex.45 |
9.9 |
0.120 |
9.9 |
0.125 |
9.9 |
0.124 |
0.04 |
Ex.46 |
10.0 |
0.125 |
10.0 |
0.127 |
9.9 |
0.126 |
0.03 |
Ex.47 |
9.9 |
0.118 |
9.9 |
0..119 |
9.8 |
0.120 |
0.03 |
Ex.48 |
9.8 |
0.120 |
9.9 |
0.125 |
9.9 |
0.123 |
0.05 |
Ex.49 |
10.1 |
0.124 |
10.1 |
0.125 |
10.0 |
0.126 |
0.04 |
Ex.50 |
8.2 |
0.126 |
8.1 |
0.125 |
8.1 |
0.123 |
0.04 |
Ex.51 |
12.2 |
0.157 |
12.1 |
0.156 |
12.1 |
0.157 |
0.05 |
Ex.52 |
15.1 |
0.158 |
15.0 |
0.160 |
15.0 |
0.160 |
0.03 |
Ex.53 |
15.2 |
0.158 |
15.1 |
0.159 |
15.1 |
0.158 |
0.06 |
Ex.54 |
12.1 |
0.123 |
12.0 |
0.120 |
12.1 |
0.120 |
0.04 |
Ex.55 |
11.9 |
0.126 |
12.0 |
0.124 |
12.0 |
0.123 |
0.06 |
Ex.56 |
11.9 |
0.119 |
12.1 |
0.120 |
12.0 |
0.123 |
0.04 |
Ex.57 |
12.1 |
0.126 |
12.0 |
0.124 |
12.1 |
0.123 |
0.03 |
Ex.58 |
24.9 |
0.158 |
25.0 |
0.159 |
24.9 |
0.157 |
0.05 |
Ex.59 |
25.0 |
0.154 |
24.8 |
0.156 |
24.8 |
0.155 |
0.05 |
[Table 15]
|
Average Thickness A |
Thickness Accuracy A (standard deviation) |
Average Thickness B |
Thickness Accuracy B (standard deviation) |
Average Thickness C |
Thickness Accuracy C (standard deviation) |
AC Layer Thickness |
Comp.Ex.17 |
14.9 |
0.288 |
15.0 |
0.290 |
15.00 |
0.294 |
0.06 |
Comp.Ex.18 |
15.0 |
0.300 |
14.9 |
0.312 |
15.10 |
0.298 |
0.04 |
Comp.Ex.19 |
14.9 |
0.314 |
15.0 |
0.320 |
15.00 |
0.316 |
0.05 |
Comp.Ex.20 |
15.1 |
0.333 |
15.1 |
0.329 |
15.00 |
0.326 |
0.05 |
Comp.Ex.21 |
14.8 |
0.228 |
14.9 |
0.225 |
14.90 |
0.230 |
0.06 |
Comp.Ex.22 |
15.0 |
0.245 |
15.0 |
0.242 |
14.90 |
0.240 |
0.08 |
Comp.Ex.23 |
15.1 |
0.256 |
15.1 |
0.252 |
15.10 |
0.252 |
0.04 |
Comp.Ex.24 |
14.9 |
0.279 |
15.1 |
0.276 |
14.90 |
0.280 |
0.06 |
Comp.Ex.25 |
15.2 |
0.276 |
15.2 |
0.280 |
15.10 |
0.282 |
0.05 |
Comp.Ex.26 |
12.1 |
0.231 |
12.1 |
0.230 |
12.00 |
0.228 |
0.06 |
Comp.Ex.27 |
12.0 |
0.259 |
12.0 |
0.254 |
11.90 |
0.252 |
0.04 |
Comp.Ex.28 |
12.0 |
0.288 |
12.2 |
0.290 |
12.10 |
0.292 |
0.05 |
Comp.Ex.29 |
11.9 |
0.228 |
11.9 |
0.232 |
12.00 |
0.230 |
0.04 |
Comp.Ex.30 |
15.1 |
0.335 |
15.2 |
0.338 |
15.10 |
0.334 |
0.05 |
Comp.Ex.31 |
12.1 |
0.455 |
12.2 |
0.460 |
12.00 |
0.450 |
0.05 |
Comp.Ex.32 |
11.8 |
0.510 |
12.0 |
0.516 |
12.00 |
0.507 |
0.05 |
Comp.Ex.33 |
12.2 |
0.500 |
11.9 |
0.505 |
12.10 |
0.501 |
0.05 |
Comp.Ex.34 |
11.9 |
0.402 |
12.1 |
0.413 |
12.00 |
0.410 |
0.05 |
Comp.Ex.35 |
12.0 |
0.452 |
12.0 |
0.450 |
12.00 |
0.459 |
0.05 |
Comp.Ex.36 |
12.0 |
0.479 |
11.9 |
0.469 |
12.00 |
0.475 |
0.05 |
[Table 16]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Ex.29 |
57.0 |
53.2 |
53.5 |
69.8 |
16.6 |
90.5 |
84.5 |
91.0 |
106.2 |
21.7 |
2.5 |
3.3 |
2.1 |
2.0 |
2.98 |
10.0 |
○ |
Ex.30 |
67.0 |
57.3 |
55.2 |
79.2 |
24.0 |
94.0 |
82.5 |
92.8 |
112.3 |
29.8 |
2.9 |
4.2 |
2.4 |
2.2 |
2.98 |
8.4 |
○ |
Ex.31 |
70.0 |
54.5 |
52.0 |
70.6 |
18.6 |
90.5 |
95.5 |
100.0 |
112.5 |
22.0 |
3.9 |
4.4 |
2.2 |
1.9 |
3.00 |
9.6 |
○ |
Ex.32 |
71.5 |
52.3 |
52.8 |
72.6 |
20.3 |
94.0 |
86.0 |
92.8 |
113.5 |
27.5 |
3.8 |
4.3 |
2.3 |
2.1 |
3.00 |
8.8 |
○ |
Ex.33 |
67.0 |
57.5 |
80.3 |
61.5 |
22.8 |
116.5 |
98.1 |
109.0 |
127.3 |
29.2 |
4.1 |
4.6 |
2.0 |
1.9 |
2.99 |
8.2 |
○ |
Ex.34 |
70.0 |
54.0 |
52.0 |
70.6 |
18.6 |
90.5 |
83.4 |
91.0 |
106.5 |
23.1 |
2.1 |
2.4 |
2.1 |
1.9 |
2.98 |
9.4 |
○ |
Ex.35 |
Used Polyamide-Based Film of Example 29 |
9.0 |
○ |
Ex.36 |
57.4 |
57.4 |
53.5 |
69.6 |
16.1 |
96.4 |
90.4 |
93.8 |
111.8 |
21.4 |
2.3 |
2.4 |
2.2 |
2 |
3.00 |
9.0 |
○ |
Ex.37 |
59.0 |
52.4 |
51.5 |
66.6 |
15.1 |
89.5 |
82.1 |
90.0 |
101.9 |
19.8 |
2.5 |
3.2 |
2.3 |
2.1 |
3.01 |
9.8 |
○ |
Ex.38 |
65.4 |
59.4 |
53.8 |
77.9 |
24.1 |
93.7 |
81.2 |
94.8 |
108.1 |
26.9 |
3.5 |
4.1 |
2.2 |
2.0 |
2.99 |
8.6 |
○ |
Ex.39 |
65.3 |
53.5 |
51.3 |
68.9 |
17.6 |
89.6 |
94.5 |
101.7 |
108.1 |
18.5 |
3.9 |
4.8 |
2.3 |
1.9 |
2.98 |
9.9 |
○ |
Ex.40 |
66.5 |
51.0 |
52.8 |
72.7 |
21.7 |
97.4 |
83.3 |
91.5 |
109.6 |
26.3 |
3.9 |
4.3 |
2.3 |
2.2 |
2.98 |
8.7 |
○ |
Ex.41 |
65.0 |
57.5 |
79.4 |
63.7 |
21.9 |
117.2 |
94.8 |
107.8 |
124.7 |
29.9 |
4.3 |
4.9 |
2.2 |
1.9 |
3.00 |
8.6 |
○ |
Ex.42 |
64.0 |
53.5 |
49.4 |
67.8 |
18.4 |
88.4 |
81.8 |
89.2 |
103.1 |
21.3 |
2.2 |
2.6 |
2.3 |
1.9 |
2.97 |
9.9 |
○ |
Ex.43 |
Used Polyamide-Based Film of Example 36 |
9.4 |
○ |
[Table 17]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Ex.44 |
56.5 |
51.2 |
53.8 |
67.8 |
16.6 |
91.0 |
83.9 |
93.5 |
103.6 |
19.7 |
2.7 |
3.1 |
2.3 |
2.0 |
2.98 |
9.9 |
○ |
Ex.45 |
64.8 |
59.0 |
56.4 |
75.8 |
19.4 |
100.8 |
93.5 |
89.7 |
114.3 |
24.6 |
3.6 |
4.2 |
2.4 |
2.1 |
2.99 |
9.4 |
○ |
Ex.46 |
73.5 |
63.2 |
50.4 |
68.6 |
23.1 |
113.5 |
90.4 |
86.5 |
107.4 |
27.0 |
3.9 |
4.4 |
2.3 |
2.0 |
2.98 |
8.6 |
○ |
Ex.47 |
59.8 |
58.9 |
55.4 |
74.3 |
18.9 |
100.7 |
92.6 |
86.4 |
113.8 |
27.4 |
3.8 |
4.3 |
2.4 |
2.2 |
2.97 |
8.9 |
○ |
Ex.48 |
71.3 |
56.1 |
78.8 |
60.7 |
22.7 |
105.6 |
90.2 |
110.4 |
118.5 |
28.3 |
4.2 |
4.7 |
2.3 |
2.1 |
2.98 |
8.7 |
○ |
Ex.49 |
72.1 |
55.8 |
51.4 |
68.7 |
20.7 |
112.6 |
83.1 |
90.8 |
108.7 |
29.5 |
2.1 |
2.6 |
2.1 |
1.8 |
3.01 |
9.5 |
○ |
Ex.50 |
56.8 |
53.8 |
55.2 |
69.1 |
15.3 |
92.7 |
83.6 |
90.1 |
111.1 |
27.5 |
3 |
3.4 |
2.3 |
2 |
3.00 |
9.9 |
○ |
Ex.51 |
59.6 |
55.4 |
51.9 |
74.5 |
22.6 |
96.7 |
89.3 |
87.9 |
115.7 |
27.8 |
2.4 |
3 |
2.2 |
2 |
2.99 |
8.7 |
○ |
Ex.52 |
52.9 |
55.4 |
56.4 |
70.1 |
17.2 |
90.0 |
92.6 |
91.0 |
113.8 |
23.8 |
3.6 |
4.2 |
2.4 |
2.2 |
2.98 |
9.1 |
○ |
Ex.53 |
54.6 |
55.0 |
59.4 |
72.8 |
18.2 |
82.9 |
86.9 |
90.7 |
110.0 |
27.1 |
2.7 |
3.6 |
2.0 |
1.8 |
3.00 |
9.5 |
○ |
Ex.54 |
52.4 |
54.2 |
59.1 |
72.1 |
19.7 |
82.9 |
85.9 |
90.3 |
109.8 |
26.9 |
3.9 |
4.4 |
2.5 |
2.2 |
3.01 |
9.4 |
○ |
Ex.55 |
53.8 |
56.7 |
62.1 |
73.7 |
19.9 |
86.7 |
88.0 |
96.7 |
111.7 |
25.0 |
2.6 |
3.2 |
1.9 |
1.9 |
2.99 |
9.5 |
○ |
Ex.56 |
54.2 |
52.7 |
58.4 |
72.4 |
19.7 |
92.6 |
86.9 |
94.2 |
112.7 |
25.8 |
3.5 |
4.0 |
2.4 |
2.1 |
2.99 |
9.5 |
○ |
Ex.57 |
58.7 |
56.2 |
64.8 |
76.0 |
19.8 |
98.4 |
88.0 |
104.8 |
114.7 |
26.7 |
3.4 |
4.2 |
2.5 |
2.1 |
2.97 |
9.6 |
○ |
Ex.58 |
53.9 |
74.5 |
76.8 |
54.6 |
22.9 |
86.7 |
109.6 |
117.5 |
89.5 |
30.8 |
3.5 |
2.9 |
2.2 |
2.0 |
2.99 |
8.6 |
○ |
Ex.59 |
56.3 |
78.3 |
79.6 |
65.3 |
23.3 |
88.9 |
108.2 |
119.2 |
92.6 |
30.3 |
3.7 |
3.0 |
2.4 |
2.1 |
3.00 |
8.5 |
○ |
[Table 18]
|
Stress at 5% Elongation |
Stress at 15% Elongation |
Boiling Water Shrinkage |
Modulus of Elasticity |
Relative Viscosity |
Draw Depth |
Wet heat Resistance |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
45° |
TD |
135° |
Stress Difference |
MD |
TD |
MD |
TD |
Comp.Ex.17 |
57.2 |
47.3 |
53.5 |
83.6 |
36.3 |
97.0 |
88.3 |
93.5 |
130.9 |
42.6 |
5.1 |
5.5 |
1.4 |
2.6 |
3.01 |
3.9 |
X |
Comp.Ex.18 |
92.4 |
50.2 |
53.5 |
56.0 |
42.2 |
140.6 |
86.0 |
93.5 |
96.0 |
54.6 |
2.7 |
3.4 |
3.3 |
2.7 |
2.99 |
2.1 |
X |
Comp.Ex.19 |
57.9 |
50.8 |
88.8 |
52.8 |
38.1 |
99.8 |
96.7 |
138.7 |
97.8 |
42.0 |
5.8 |
6.3 |
1.4 |
2.7 |
2.98 |
3.5 |
X |
Comp.Ex.20 |
62.4 |
55.6 |
56.4 |
91.0 |
35.4 |
104.8 |
95.4 |
96.4 |
135.6 |
40.2 |
5.5 |
6.1 |
3.1 |
1.3 |
3.00 |
3.2 |
X |
Comp.Ex.21 |
77.9 |
48.0 |
46.3 |
84.3 |
38.0 |
117.9 |
92.4 |
90.4 |
134.2 |
43.8 |
5.1 |
5.3 |
2.5 |
2.8 |
2.97 |
3.5 |
X |
Comp.Ex.22 |
60.1 |
52.4 |
54.0 |
92.4 |
40.0 |
110.3 |
90.2 |
93.5 |
132.4 |
42.2 |
5.2 |
5.4 |
3.3 |
1.4 |
2.98 |
3.0 |
X |
Comp.Ex.23 |
78.2 |
47.9 |
50.2 |
79.9 |
32.0 |
124.6 |
97.5 |
100.3 |
141.2 |
43.7 |
5.8 |
6.5 |
1.4 |
1.5 |
2.99 |
4.2 |
Δ |
Comp.Ex.24 |
84.9 |
59.8 |
50.4 |
60.0 |
34.5 |
138.5 |
103.4 |
91.0 |
110.0 |
47.5 |
5.5 |
6.2 |
3.2 |
1.4 |
2.99 |
4.6 |
Δ |
Comp.Ex.25 |
47.6 |
54.6 |
87.4 |
53.2 |
39.8 |
87.5 |
96.5 |
137.7 |
93.7 |
50.2 |
6.2 |
6.4. |
2.5 |
1.4 |
2.98 |
3.0 |
X |
Comp.Ex.26 |
56.7 |
48.5 |
52.0 |
86.7 |
38.2 |
96.5 |
86.7 |
92.1 |
128.6 |
41.9 |
5.0 |
5.4 |
1.3 |
2.7 |
3.00 |
3.5 |
X |
Comp.Ex.27 |
91.2 |
49.8 |
53.6 |
56.1 |
41.4 |
138.4 |
84.2 |
91.5 |
94.6 |
54.2 |
2.8 |
3.4 |
3.3 |
2.8 |
3.00 |
4.5 |
Δ |
Comp.Ex.28 |
56.4 |
49.7 |
86.3 |
53.0 |
36.6 |
100.2 |
94.5 |
134.0 |
99.6 |
39.5 |
5.6 |
6.2 |
1.3 |
2.7 |
2.98 |
4.1 |
Δ |
Comp.Ex.29 |
63.8 |
55.4 |
58.7 |
92.4 |
37.0 |
102.2 |
96.8 |
99.1 |
139.6 |
42.8 |
5.5 |
6.0 |
3.2 |
1.4 |
2.98 |
3.0 |
X |
Comp.Ex.30 |
92.6 |
73.9 |
102.8 |
120.0 |
46.1 |
112.6 |
92.6 |
134.5 |
154.0 |
61.4 |
1.4 |
2.3 |
3.4 |
2.0 |
2.98 |
2.1 |
X |
Comp.Ex.31 |
55.8 |
90.7 |
88.0 |
58.4 |
34.9 |
82.6 |
125.0 |
124.6 |
85.4 |
42.4 |
2.5 |
3.2 |
1.5 |
2.1 |
2.99 |
3.4 |
X |
Comp.Ex.32 |
51.9 |
74.5 |
86.4 |
54.0 |
34.5 |
88.4 |
96.8 |
129.0 |
117.4 |
40.6 |
2.7 |
3.3 |
3.1 |
2.8 |
2.99 |
2.5 |
X |
Comp.Ex.33 |
59.3 |
98.4 |
108.9 |
76.1 |
49.6 |
83.6 |
130.0 |
129.7 |
91.7 |
46.4 |
5.2 |
5.1 |
1.3 |
2.7 |
3.00 |
2.9 |
X |
Comp.Ex.34 |
72.6 |
51.2 |
60.7 |
91.8 |
40.6 |
89.7 |
81.9 |
115.6 |
125.4 |
43.5 |
2.8 |
3.7 |
3.3 |
2.6 |
2.98 |
3.1 |
X |
Comp.Ex.35 |
82.6 |
51.8 |
54.9 |
91.9 |
40.1 |
91.6 |
79.0 |
86.7 |
123.4 |
44.4 |
3 |
3.5 |
3.3 |
2.6 |
2.98 |
2.6 |
X |
Comp.Ex.36 |
52.0 |
87.9 |
94.3 |
58.1 |
42.3 |
79.6 |
112.0 |
126.8 |
88.6 |
47.2 |
5.3 |
5.1 |
3.1 |
2.6 |
3.00 |
3.0 |
X |
[0154] In Tables 13 to 18, average thickness is in units of "µm", AC layer thickness is
in units of "µm", stress is in units of "MPa", boiling water shrinkage is in units
of "%", modulus of elasticity is units of "%", and draw depth is in units of "mm".
[0155] In Examples 29 to 59, since the draw ratios of the polyamide-based films in particular
are within a specified range, the difference between the maximum value and minimum
value of stress at 5% elongation in the 0 degree direction (MD), 45 degree direction,
90 degree direction (TD) and 135, degree direction in uniaxial tensile tests of the
resulting polyamide-based films was 35 MPa or less while the difference between the
maximum value and minimum value at 15% elongation was 40 MPa or less. Laminates obtained
using these polyamide-based films demonstrated high Erichsen values and had uniform
ductility in all directions during cold forming. In other words, the polyamide-based
films of each of Examples demonstrated superior moldability without the occurrence
of problems such as breakage of the aluminum foil, delamination or the formation of
pinholes.
[0156] In addition, since the polyamide-based films obtained in Examples 29 to 59 have a
primer layer containing an anionic water-dispersible polyurethane resin on one side
thereof, laminates using these polyamide-based films were determined to have excellent
moisture heat resistance.
[0157] On the other hand, in Comparative Examples 17 to 36, since the draw ratios of the
polyamide-based films in particular do not satisfy a specific range, the above-mentioned
A and B values in four directions formed of the 0 degree direction, 45 degree direction,
90 degree direction and 135 degree direction do not satisfy the requirements of the
present invention. Accordingly, laminates obtained using these polyamide-based films
of the comparative examples demonstrate low Erichsen values and have inferior moldability
as a result of failing to have uniform ductility in all directions during cold forming.